”an"... ‘~ My} . .‘, .12 4 -.\..4. "'1' In '1, fl. 1. ' w . ' ‘ ( r“; r V W "I", \— w...\,,_ . ”4.“, """u‘, .... a -4-..., "nr ”u???" “WK“? '~ 5-;2'. , huh,“ rut: n, _ 1' “"‘mw 1 ‘f‘f' , , ‘ m, . ' q, _ ’ I" Ian: ‘*‘ u .m- u,.. ; . way. I V1". . lmuIn!"llljwwfluflmuuflyuHymn 5 This is to certify that the dissertation entitled Synthesis of Chi Applications to As and Selective ral Catalysts and Their ymmetric Cross-Coupling Reactions Hydrogenation presented by Hussein Ali / has been accepted towards fulfillment of the requirements for __Eth+______degnmin' Chemistry \ of: (79,, c. H. Bruéeker) M\ ajor professor Date 2-22—90 ________________ MS U is an Affirmative Action/Equal Opportunity Institution 0 12771 \,‘ . 7 , , PLACE IN RETURN BOX to remove this checkout from your record. To AVOID FINES return on or before date due. DATE DUE DATE DUE DATE DUE MSU Is An Affirmative Action/Equal Opportunity Institution SYNTHESIS OF CHIRAL CATALYSTS AND THEIR.APPLICATION TO ASYMMETRIC CROSS-COUPLING REACTIONS AND SELECTIVE HYDROGENATION BY Hussein MOhamed Galal El-Din Ali A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of _DOCTOR or PHILOSOPHY Department of Chemistry 1990 otOIIQ/ ABSTRACT SYNTHESIS OF CHIRAL CATALYSTS AND THEIR.APPLICATION TO ASYMMETRIC CROSS-COUPLING REACTIONS AND SELECTIVE HYDROGENATION BY Hussein MOhamed Galal El-Din Ali Asymmetric catalysis is one of the most impressive achievements to date in catalytic selectivity. In this work, new series of chiral Ni complexes of amine thioether and selenoether have been generated in situ and used as catalysts for asymmetric Grignard cross-coupling reactions. Their structures are (R,S)-(n5-C5H5)Fe(n5-C5H3-l— CH(Me)NMe2-2-SR)(NiC12) where R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu, i-Pent, 82, Ph, and 4-Tolyl, (R—S)- z N 140 NR2 I 14C N92=N5t2 14d NRZ:NBU2 OH f\/ 146: NR2: N y/\ 14f? NR2: N ”’\0H Ligands Prepared for Asymmetric Synthesis. 1951;21 it was prepared by the reaction of cyclopentadienyl magnesium bromide with anhydrous iron (III) chloride. However, its true structure was established later by Wilkinson22 for which he earned a Nobel Prize for chemistry in 1973. Since then ferrocene has generated rich chemistry mainly due to its stability and unusual reactivity. The two main routes to the thousands of known substituted ferrocenes are synthesized through electrophilic substitution and metallated ferrocenes. Ferrocene is more reactive toward electrophilic reagents than benzene. It undergoes Friedel-Crafts alkylation, acylation, Vilsmeier formylation, Mannich mercuration, sulfonation, and aminomethylation. The elerophilic substitution chemistry of ferrocene has been reviewed23'24 and representative reactions are shown in scheme 2. The products of these reactions are useful starting materials by elaboration of ring substitunets. The only limitation of electrophilic substitution is the oxidation of ferrocene (FcH) to ferricinium ion (FcH)+ by the electrophilic reagents. Sulfonation for example can not be affected by concentrated sulfuric acid; however, it can be carried out by using chlorosulphonic acid in acetic anhydride with the SO3-dioxane complex.25 Alkylation can occur under Friedel- Crafts conditions but with low yield (Ca. 30%),24 while direct nitration and halogenation cannot be carried out; therefore, the second route to substituted ferrocene is Fe N-iodosuccinamide 9 /© © @+ HQCACJZ CH3 COCI AiCI3 ©C LiCl or Ac208F3 3©e HCN OF HF AFN+ 2,H2SO4 Me NCH CH2 NMe2 Fe 2 2 CICONPh2 thCCH3DCHO <1::E::>2 AICIB POCI3 or AICI3 CISO 3H AC 20 CONPh2 CICOSR SO 3-dioxane AICI3 © as @/ ©/ COSR COOH (Mi Fe Scneme 2: Electropnilic Subistitution Reactions of Ferrocene. required, which is via metallation. Ferrocene was lithiated by 1.04 molar equivalents of n- butyllithium to give mainly monolithioferrocene 17,26 while using two equivalents of n-butyllithium in tetramethyl- ethylenediamine (TMEDA) gave over 90% dilithioferrocene species 18, which could be isolated as a pyrophoric red- orange crystals.27 Preparation and examples of synthetic applications of mono- and dilithioferrocene are shown in scheme 3. Ferroceneboric acid 19 is an important intermediate for the preparation of chloro, bromo-, amino-, and hydroxyferrocenes28 or substituted ferrocenes.29 Lithiation of N,N-dimethylaminomethyferrocene 20 is easier than it is with ferrocene (eq. 1).30 The lithiated product 21 is useful intermediate for preparing many bidentate ligands as shown in scheme 4. Fe . Fe Li © 4© T20) (21) ON X I: I (D C F i 3 I (D C r \ F /—\ ——z > m I) m 0 Fe ——> Fe ——-T—-———> Fe /-———> Fe MEDA \N © ©sz ©Asn2 17 18 //N\ 138COHj3orCE-Bu0338 23H2O PR2CI (’7 BCOH) N 2 @— Fe CuCI2 Fe CuCEienzamide)2 Fe 0 @— ‘—_ A PR © '© 2 19 - KOH Hg:;j/// CU(OAC)2 NH @— 2 F Fe H30. © X 9 @319) @ e Fe ‘X2—© _—’© Ti m @ Scheme 3' Synthesis And Reactions of Mono- And Dilithioferrocene. \J Fe NMe2 ’ l « © Fe NMe2 NMe @ c I SiMe3 © E3 HO O NMe NMe R252 NMe Fe 2 4 Fe 2 2 21 C | Pphz BCOBU)3 OH Ph Ph Fe NMe2 Scneme 4f Reactions Of 1-DimethylaminoethyI-2—Iitnioferrocene. Chiral N,N-dimethylaminoethylferrocene 22 was first prepared and resolved by Ugi et al., as outlined below.31 It O OH Fe Fe Fe CH3COCI NaH2AICOCH2CH2OCH332 © AI(Z|3,CH2CI2 © C6H6 @ HOAC/C H, e V H M Me OAC Fe Fe Fe ReSOIution HNMe /CH30H 2 A A V L-tartar IC acid _n)-22 was also lithiated32 with n-butyllithium stereoselectively as shown in eq.2. This procedure has been used in this work and by Kumada and Co—workers to prepare many chiral ferrocenylamine phosphine ligands.2'20'33'36 :J CED-CBJ-23 (FD-C5}??? Examples of the synthesis of ferrocenylphosphine are depicted in scheme 5. Transition metal complexes of these ligands proved to be successful catalysts for asymmetric hydrogenation of olefins37 and ketones,38 hydrosylation of ketones,39 allylic alkylation,4O allylic amination,41 aldol 42 43 condensation, and Grignard cross-coupling reactions. B. Asymmetric Cross-Coupling Reactions. 44 45 Since Corriu and Kumada independently reported in 1972 that the cross-coupling of Grignard reagents with aryl and alkenyl halides could be markedly catalyzed by certain nickel-phosphine complexes, e.g. C12Ni(PPh3)2, a wide range of cross-coupling reactions have been developed and some of them used in great success in synthetic organic chemistry.46 Consequently, the cross-coupling reactions have been extended to include different electrophilic reagents such as 47 48 49 and aryl and alkenyl ethers, sulfides, selenides, phosphates.50 Different organometallic reagents have also been prepared and varied to include metals less electropositive than Li51 and Mg such as B,52 Al,53 Si,54 Sn,55 and Zr.56 Organometallics containing these metals are known to be more compatible with various electrophiles, such as esters, amides, nitriles, and nitro compounds (eq.3).57 13n- BuLi/Et 20© 23ClSiMe H:‘(/2///22 SIM93 (5)-c3) 1)n-BuLi/Et20 23CIPPh2 t—euox DMSO ppn2 NMe2 © CPD-CBD-PPFA 16 Scheme 5; Me HI!” eppnz ppn2 1jn- BULi/Et20= ©e é—Ppnz 1)n— BuLi 2)CIPPh2 1jn- BULi/Et2 R PPFA 23n- BULi/TMEDA C-) (E) 2)H20 CB)-g§)-BPPFOH 3)C|PPh216 H2 PPn2 -—-———————o» <2:§:§>>—-:DN2A (nj-(SD-BPPFOAC (20) Al2 MeOH PPh2 eppn2 H2/[Rh] (RD-(Sj-BPPFA 24 14 (8,20,37,41) 140‘ NH 14C? anzNEtz 14d? NR2=NBU2 Et i PPh Fe 2 H 14c: NFI2=N’\'/O “\b ppn2 / H 25 14f: NR -N Synthesis of Optically Active Ferrocenylphosphines. ll R-m -k Rq-X 44>. R-R1 +- inX C3) M=Ni,Pd m=Mg,Li,Zn,AI,zr,B,Sn,Hg quaryl,alkenyl X:C|,Br,l,OR,SR,SeR,OPCOjCOR32 Although organometallic reagents with methyl, aryl, alkenyl, benzyl, or alkynyl groups have been used successfully for cross-coupling reactions, those with alkyl groups containing B-hydrogen(s) usually undergo isomerization of the alkyl group and/or reduction of the halides;58 however, dichloro [1,l'-bis(diphenylphosphino)- ferrocene]palladium(II) [PdClZ(dppf)] were effective catalysts in some of these cases.46 The asymmetric cross-coupling reaction most extensively studied so far is the coupling of 1-phenylethylmagnesium chloride 27 with vinyl bromide 28 yielding 3-phenyl-1-butene 29 (eq.4). The reaction generally proceeds in ether at 00C in the presence of a Ni- or Pd—phosphine catalyst. M/Lx * Ph-CH—MgCI + CH2=CHBF =z Pn-CH—CH=CH2 (4) Qe we 27 28 29 12 Kumada's group has found that ferrocenylamine phosphines complexed to nickel or palladium chloride are efficient ligands, giving rise to the product 29 with up to 65% ee.35 The data obtained with the ferrocenylphosphine ligands have led to the following significant featureszgr35 (a) the ferrocene planar chirality plays a more important rule than the carbon central chirality on the side chain of the ferrocene in determines the configuration and optical purity of the product. (b) The optical yield decreased dramatically when (R)-PPEF 26 was used as a ligand, indicating that the amino group is of primary importance for high stereo- selectivity. The presence of a methoxy group instead of an amino group as in PPFOMe, 13, gave nearly the same efficiency (57% ee). (c) The stereoselectivity is not changed significantly by the introduction of different aryl rings to the phosphino group but is strongly affected by changing the steric bulk of the amino group. The chiral B-(dimethylamino) alkylphosphines 12 derived from amino acids are more effective than the ferrocenyl- phosphine ligands that gave product 29 with up to 83% optical yield.59 The proposed mechanism of Grignard cross-coupling 3 is presented in scheme 6, which include oxidative reactions addition of the organic halide to the low valent group 10 metal, a transmetallation of an organometallic reagent with the transition metal halide, isomerization to cis isomer, l3 and reductive elimination of the product. The oxidative addition reaction is often stereospecific, proceeding with inversion of configuration at a sp3 carbon or retention of 2 carbon. Both transmetalation and reductive geometry at sp elimination steps occur with retention of configuration at carbon.35 The chiral Grignard reagents undergo racemization because of the stereochemical instability of the carbon-Mg RX + Fl\ m ______. R—R\ + mX R—R\ LnMCOJ RX 010 n-2L L L l '2... n-M2*-L P-M -X I 8 fi\ L 08(16e) d (16e) R\m L ‘ R-m2*-R\ mX I L d8(16e) SCheme 6' Catalytic Cycle for Grignard Cross-C0upling Reactons. bond, and if the inversion at this chiral carbon is much faster than that of cross-coupling reaction, the optical purity of the coupling product should be kept constant throughout the reaction since the Grignard reagent always exists in a racemic form (eq.5) and accordingly, the optical purity and the configuration of the coupling product are determined primarily during this step.35 l4 R1 fast R1 93X 9, >——MgX 4> XMg—~< > ér—R3 CS) ; +__—— ; * \\ 92$ 1+2 [ML ] Rzg racemic mixture optically active There are still only few catalytic cross-coupling reactions reported to provide optical yields over 80%; some of these examples are presented in eq. 6-8.3'6OI61 One of the most exiting applications of the asymmetric Grignard cross-coupling reaction is the preparation of optically active allylsilanes (eq.9).62 It is well- documented that allylsilanes are useful intermediates in 54,63 organic synthesis, undergoing reactions with a wide range electrophiles in a regiospecific manner. MgCl H41 Me (SjValphos + 4?\Br —:————————. | NiCl2 94%99 CS)ValphOS MgCl + 4?\Br —:————————> * NiC|2 \ 80%ee Ph ZnX Ph * PGCI n — s -PPFA \T/ + 45\Br 2[C_D C_) J= \r/§> (8) Me Me 85%ee “935‘ POCIZEC83—(§j—PPFA] pn E‘Mea (9) / Ph Ph H 95%ee 15 Recently, a nickel complex of AMPHOS 39 was found to catalyze asymmetric Grignard cross-coupling reaction of 1- phenylethylmagnesium chloride with (E)-bromostyrene to yield (E)-1,3-diphenyl-l—butene in 40% ee.64 Interestingly, zinc bromide induced a switch in the configuration of the coupling product shown in eq.4 catalyzed by nickel or palladium complexed to ligands derived from amino acids 12. The addition of ZnBr2 reversed the enantioselection but did not affect much the optical yields.65 Cross-coupling of 2—methyl-l—naphthylmagnesium bromide 30 with 1,5-dibromonaphthalene 31 was reported very recently in the presence of (S)-(R)—PPFOMe/NiC12 (eq.10.) to give the coupling product 32 in 98.7% ee.66 Br I I Me I I Me CS)-(R)-PPFOMe/Ni8r2 + ' _ = + (10) Me MgBr Br Me Me .. 00 CO 84:16 (9,93-32 98.7%ee meso-32 16 C. Selective Homogeneous Catalytic Hydrogenation of Olefins. Homogeneous catalytic hydrogenation of organic substrates is an important class of organometallic chemistry. Many functional groups have been hydrogenated, e.g. acetylenes, aldehydes, ketones, nitro, and arenes; however, olefins are the most studied substrates. A large number of homogeneous hydrogenation catalysts have been developed 67, but only a few are useful in organic synthesis. The majority of these catalysts are coordinatively unsaturated to accommodate substrate complexation and H2 oxidative addition. Examples of these catalysts are Co(CN)53-,68 C02(CO)8-di(tertiary phosphine),69 [RuH(COD)(PMeZPh)3][PF6],7O [Cplc0)3Cr]2,7l methyl benzoate-Crlc0)3,72 IrCl(CO)(PPh3)2 (Vaska's complex),73 and (Ph3P)3RhCl (Wilkinson's catalyst).74 Metal hydrides have also been used instead of molecular H2 in catalylic hydrogenation; examples are LiAlH4/CuI,75 diisobutylaluminum hydride (DIBAH)/MeCu,76 PhZSiHZ/Pd(0)/ ZuC12(cat.),77 Mg/MeOH78 and different transition metal hydrides.79 Modification of Wilkinson's catalyst, (Ph3P)3RhCl, by incorporation of chiral phosphines has led to spectacular enantiomeric excesses. Optical yields over 80% are frequently obtained using chiral bidentate phosphine ligands complexed mainly to rhodium as catalyst for the hydrogenation of a-acylaminocinnamic or acrylic acids or esters, as shown in eq.ll, or any other substrate that meets 17 the following requirementsz3'9 (a) a substituent containing a basic carbonyl group (e.g. NHCOR, OCOR, CHZCOOR) located 8 to the double bond. (b) An electronegative substituent (e.g. COOR, CN, C6H5) on the a carbon atom. (c) A hydrogen atom in H \ /COOP Rh/L* * coon : ———> /C C\ + H2 PhCH2 H [113 Ph NHCOCH3 NHCOCH3 (AC) RzH 33a 34 (MAC) RzMe 330 CEAC] RzEt 33c any of the remaining two positions of the double bond. The obligatory carbonyl group coordinates to the rhodium atom, as does the double bond, to form a catalyst-substrate chelate complex. This, rigid system is responsible for the high optical yields obtained. Therefore, any substrate that satisfies these requirements can be asymmetrically hydrogenated with different catalysts with high enantiomeric excesses . Few reports could minimize these substrate requirements.37'80 Ferrocenylamine phosphines, again, showed their superiority. (R)—N—Methyl—N—[2-dialkylamino)ethyl]~1- [(S)-l,2-bis(diphenylphosphino) ferrocenyl]ethylamines 14a gave rise to high stereoselectivity as well as high catalytic activity in the hydrogenation of trisubstituted l8 acrylic acids 35 (tetrasubstituted olefins) where high stereoselectivity has never been observed; thus, two chiral centers could be created in one reaction with up to 97% ee as presented in eq.12.37 8\C/Me CR)-CS)_14a/Rh E + H2 ‘ _ > (12) Pn’ \COOH 35 R:Et,Ph Halpern and Coworkers81 have studied mechanistically and kinitically the asymmetric hydrogenation in details and proposed the catalytic cycle presented in scheme 7. Three intermediates 37, 38, 40 have been intercepted and characterized by multinuclear NMR and x-ray crystallography.82'83 The crucial experiment that revealed the origin of the enantioselectivity was the determination of the structure of the predominant diastereomer of [Rh(S,S- CHIRAPHOS)[EAC]+ ion, where EAC is ethylacetylamino- cinnamate, by x-ray analysis of single crystals of the perchlorate salt. Addition of H2 should occur to the Rh- coordinated face of the olefin in the Rh-olefin adduct. That would yield N-acetyl-(S)-phenylalanine ethyl ester whereas the predominant product was the R isomer and led to the conclusion that the major product enantiomer was derived from the minor (i.e. 19 less stable) diastereomer of the catalyst-substrate adduct, by virtue of its much higher reactivity relative to that of the major (more stable adduct).81 Ph p" [:::C7 Pn ph Pnpn C, Ph pn 37 COOCH3 pncuzcu \ NHCOCH3 P\h/ Pn H n/f'chlll :Ph Pnph MeOH (5) + noroornane pnpn 34 ... H COOCH3 \/ l pn NHCOCH3 { an NH °CH3 ‘ f\ 02% ‘ Ph Ph ‘CH 3 as [H23 4. phan p“ H / s 9h"' 00H3 ‘ p NH \ P’n ph 0=cl \ 3g CH3 Scneme 7: Catalytic Mechanism for The Hydrogenation of Methyl-(Z)- a-Acetamidocinnamate (MAC) by Using Diphosphine Rhodium Catalysts. 20 EXPERIMENTAL Air-sensitive reagents were manipulated in a prepurified argon atmosphere. Standard Schlenk-ware techniques and a vacuum line were employed. A nitrogen-filled glovebox was used for transfers when necessary. 1H- and l3C-NMR spectra were obtained in chloroform—d, and acetone-d6 respectively by using Bruker WM-250 or Gemini-300 spectrometer. Chemical shifts are reported in ppm downfield from a tetramethylsilane (TMS) as internal standard. Infrared (IR) spectra were recorded by use of a Nicolet 740 FT-IR or a Perkin-Elmer 599 grading spectrometer by using neat films for liquids or Nujol mules for solids between CsI or KBr plates. Mass spectra were obtained by means of Finnigan 4000 instrument. Gas chromatography was performed by using a Hewelett-Pakard 5880 A instrument. Elemental analyses were performed by Galbraith Laboratories, Knoxville, TN. Melting points were determined by means of Thomas-Hoover capillary melting point apparatus. Solvents used were A.C.S. reagent grade and were purified and dried by standard methods.84 (S)-N,N-Dimethyl-1— ferrocenylethylamine was prepared and resolved using Ugi's procedure.31 Disulfides and diselenides were obtained from Aldrich Chemical Company. Bis(benzonitrile) complexes, [(PhCN)2MC12] where M = Pd, Pt, were prepared as reported.85'86 The Grignard cross-coupling substrate, 1- 21 phenylethyl chloride, was prepared according to a published procedure;8'7 allylmagnesium chloride (2M solution in THE) was obtained from Aldrich Chemical Co. The 1H NMR chiral shift reagent, Tris(d,d-dicampholymethanato)europium(III) [Eu(dcm)3], was purchased from Alfa Products. All the hydrogenation substrates were obtained from Columbian Carbon Co., Columbian Organic Chemical Co., Alfa Products Co. and Aldrich Co. These reagents were purified by standard methods before use. A. Preparation of Ligands. (S,R)-1-(l-Dimethylaminoethyl)—2-methy1thioferrocene (41, R = Me). (S)-N,N—Dimethyl-l-ferrocenylethylamine (22 ,1.5g, 5.8 mmol) was placed in 100-mL round-bottomed Schlenk flask equipped with a side arm, stirring bar and a rubber septum. The flask was evacuated and filled with dried argon 3 times then 50 mL freshly dried ether was added via cannula. The solution was cooled to -780C and while being stirred 4.0 mL 1.6M (6.4 mmol) of n—BuLi was added dropwise Via syringe. The resulting orange suspension was stirred for 12 h at room temperature. MeZSZ (0.53 mL, 5.9 mmol) was added dropwise at -780C Via syringe. After stirring for 24 h at room temperature, 20 mL of saturated aqueous NaHCO3 was added. The resulting organic layer and ether extracts from the aqueous layer were combined, washed, dried over anhydrous 22 Na2804 and evaporated. The crude product was chromatographed on silica gel by gradient elution of hexane/ CH2C12 solvent system then recrystalyzed from CHZClZ-hexane to give yellow crystals: yield 76%; mp 64-660C. 1H NMR 8 ppm (J in H2) 4.30, 4.13 (m, C5H3); 4.09 (s, Cp); 3.92 (q, flMe, 6.9); 2.11 (S, NMez); 2.27 (S, SMe); 1.38 (d, cage, 6.9). 13c NMR 5 ppm 93.82 (5, c1); 84.11 (3, c2); 72.14 (8, c5); 70.50 (d, Cp); 68.13, 67.04 (d, c3, c4); 56.88 (a, CHMe); 40.23 (q, NMeZ); 19.88 (g, SMe); 11.09 (q, CHMe). IR (Nujol, KBr) 1279, 1261 (alkyl C-H bend); 1199 (C-N stretch); 1105 ,1015 (asymmetric ring breathing); 980 ,940 (ring-H bend parallel to ring); 821 (ring-H bend perpendicular to ring); 477 (asymmetric ring—Fe stretch). MS m/e (relative intensity), 303 (0.72, M+); 258 (37.06, M+-HN(CH3)2); 243 (22.94, M+-HN(CH3)2-Me); 121 (61.13, CpFe); 56 (67.01, Fe); 44 (100, N(CH3)2). Elemental Analysis for C15H21FeNS (calcd.); C, 59.79 (59.41); H, 7.01 (6.98). (S,R)-1—(1-Dimethylaminoethyl)-2-ethylthioferrocene (42, R = Et). The amine (5)-22 (1.5g, 5.8 mmol) was dissolved in 50 mL dry ether and placed in lOO-mL round-bottomed Schlenk. while 23 being stirred at -780C under argon, 4.0 mL n-BuLi 1.6M (6.4 mmol) was added dropwise via syringe. After stirring for overnight at room temperature, 0.73 mL Et282 (5.9 mmol) was added dropwise via syringe at -780C. The solution was allowed to reach room temperature and stirred for 24 h then 20 mL saturated NaZSO4 was added . The organic layer and the ether extracts from the aqueous layer were combained, dried and evaporated. The oily product was chromatographed on silica gel and eluted with hexane/CH2C12 to give a brown oil: yield 51%. 1H NMR 5 ppm (J in Hz), 4.34, 4.18 (m, C5H3); 4.10 (s, Cp); 3.97 (q, CHMe, 6.8); 3.00 (m, SCHZ); 2.13 (s, NMeZ); 1.39 (a, cage, 6.8); 0.96 (t, cazgg3, 7.3). 13c NMR 6 ppm 95.21 (3, C1); 80.99 (8, c2); 75.14 (d, c5); 70.86 (d, Cp); 68.76, 67.59 (d, c3, c4); 57.03 (d, CHMe); 40.41 (q, NMeZ); 31.12 (t, SCHZ); 15.49 (q, CH29H3); 10.51 (q, CHMg.) IR (neat, KBr) 2820, 2779 (alkyl C-H stretch); 1272, 1260 (alkyl C-H bend); 1200 (C-N stretch); 1105, 1015 (asymmetric ring breathing); 982, 940 (ring—H bend parallel to ring); 822 (ring-H bend perpendicular to ring); 545, 505 (asymmetric ring tilt); 475 (asymmetric ring-Fe stretch). MS m/e (relative intensity), 317 (1.58, M+); 272 (38.02, M+-HN(CH3)2); 243 (33.83, M+-HN(CH3)2—Et); 121 (72.88, CpFe); 56 (55.23, Fe); 44 (100, N(CH3)2). 24 Elemental Analysis for C16H23FeNS (calcd): C, 60.89 (60.57); H, 7.27 (7.31). (S,R)-1-(1-Dimethy1aminoethy1)-2-n-propylthioferrocene (43, R = n-Pr). The procedure was the same as for 41 except that 0.92 mL (n-Pr)282 (5.9 mmol) was used. The product after chromatographed on silica gel and eluted with hexane/CH2C12 was recrystalyzed from CH2C12-Hexane to give brownish crystals: yield 68%; mp 32-330C. 1H NMR 8 ppm (J in Hz) 432, 416 (m, C5H3); 4.10 (s, Cp); 3.97 (q, CHMe, 6.8); 2.67 (m, ScHZ); 2.13 (s, NMeZ); 1.57 (m, SCHZ—EEZ); 1.39 (d, CHME, 6.8); 0.96 (t, CHZEEB’ 73). 13c NMR 5 ppm 94.83 (3, cl); 81.16 (3, c2); 74.76 (6, c5); 70.67 (a, Cp); 68.56, 67.39 (a, c3, c4); 56.90 (a, gHMe); 40.16 (q! NMez); 39.20 (t, SCH2); 23.62 (t, SCHZEEZ); 13.76 (q, CH29H3); 10.33 (q, CHME). IR (neat, KBr) 2821, 2780 (alkyl C-H stretch); 1275, 1260 (alkyl C-H bend); 1200 (C—N stretch); 1105, 1010 (asymmetric ring breathing); 982, 939 (ring-H bend parallel to ring); 821 (ring-H bend perpendicular to ring); 545, 505 (asymmetric ring tilt); 470 (asymmetric ring-Fe stretch). MS m/e (relative intensity), 331 (4.59, M+); 316 (1.79, M+—Me); 286 (27.10, M+-HN(CH3)2); 243 (25.25, M+-HN(CH3)2- n-Pr); 121 (64.79, CpFe); 56 (49.55, Fe); 44 (100, N(CH3)2). 25 Elemental Analysis for C17H25FeSN (calcd.): C, 61.68 (61.63); H, 7.68 (7.61). (S,R)-1-(l-Dimethylaminoethyl)-2-isopenty1thioferrocene (44, R = i-Pent). The same procedure as for 41 except that 1.12 mL (5.9 mmol) of (i-Pent)282 was used. The product after column chromatography was obtained as a brown oil: yield 65%. 1H NMR 5 ppm (J in Hz) 4.31 m, 4.15 m (C5H3); 4.08 s (Cp); 4.00 q (ggme, 6.8); 2.68 m (SCHZ); 2.14 s (NMe2); 1.61 m (scazggz); 1.46 m (EEMez)i 1.41 d (cage, 6.9); 0.85 d, 0.83 d (0.26). 13c NMR 5 ppm 95.37 3 (cl); 81.17 5 (c2); 75.11 d (C5); 70.82 d (Cp); 60.80 d, 67.54 d (03, c4); 57.04 d (CHMe); 40.36 q (NMeZ); 39.82 t (SCHZ); 35.32 t (SCHZEHZ); 28.24 d (ggmez); 22.74 q (cagez); 10.16 q (CHMe). IR (neat, KBr) 2820, 2780 (alkyl C-H stretch); 1278, 1260 (alkyl C-H bend) ; 1198 (C-N stretch); 1102, 1007 (asymmetric ring breathing); 982, 939 (ring-H bend parallel to ring); 819 (ring-H bend perpendicular to ring; 541, 505 (asymmetric ring tilt); 468 (asymmetric ring-Fe stretch). MS m/e (relative intensitY), 359 (7.99, M+); 344 (2.47, M+-Me); 314 (35.50, M+-HN(CH3)2; 288 (1.36, M+-i-Pent); 243 (30.56, M+-HN(CH3)2)-i-Pent); 121 (78.39, CpFe); 56 (60.37, Fe); 44 (100, N(CH3)2). 26 Elemental Analysis for C19H29FeNS (calcd.): C, 63.91 (63.51); H, 8.13 (8.13). (S,R)-1-(l-Dimethylaminoethyl)-2-benzy1thioferrocene (45, R = 82). The amine (S)-22 (1.5 g, 5.8 mmol) was placed in a 200 mL round-bottomed Schlenk flask equipped with a stirring bar, a side arm and a rubber septum. The flask was evaculated and filled with dried argon 3 times then 50 mL dried ether was introduced. After cooling to -780C, 4.0 mL 1.6 M (6.4 mmol) n-BuLi was added slowly via a syringe. The orange suspension was allowed to reach room temperature and stirred overnight. A 1.29 g (5.9 mmol) Bz282 dissolved in 30 mL warm hexane was added dropwise via cannula at -780C. The resulting solution was allowed to reach room temperature and stirred for 12 h. A 20 mL saturated Na2804 was added then the organic layer and the ether extracts were combined, dried and evaporated. The oily residue was chromatographed on silica gel and eluted with gradiant hexane/CH2C12 solvent system. The product was obtained as a brown oil: yield 72%. 1H NMR 6 ppm (J in Hz) 7.24 m (Ph); 4.25 m, 4.13 m (C5H3); 4.08 s (Cp); 3.92 q (CHMe, 6.9); 3.95 m (SCHZ); 2.22 s (NMeZ); 1.42 d (CHMe, 6.9). 136 NMR 5 ppm 140.10 s, 129.87 d, 128.83 4, 127.22 4 (8h); 94.88 8 (C1); 80.06 8 (C2) ; 75.36 d (C5); 70.56 d (Cp); 27 68.83 d, 67.50 d (C3, C4); 57.09 d (CHMe); 40.01 q (NMeZ); 41.83 t (SCH2); 9.71 q (cng). IR (neat, KBr) 2820, 2780 (alkyl C-H stretch); 1610 (aromatic C-C stretch); 1275, 1260 (alkyl C-H bend); 1200 (C-N stretch); 1105, 1005 (asymmetric ring breathing); 980, 940 (ring-H bend parallel to ring); 910 (aromatic C-H bend out—of plane); 820 (ring-H bend perpendicular to ring); 542, 505 (asymmetric ring tilt); 470 (asymmetric ring—Fe stretch). MS m/e (relative intensity), 379 (M+) ; 334 (25.00, M+- HN(CH3)2); 243 (55.53, M-HN(CH3)2)-BZ); 121 (100, CpFe); 91 (59.95, PhCHZ); 56 (51.50, Fe); 44 (64.43, HN(CH3)2). Elemental Analysis for C21H25FeNS (calcd.): C, 66.59 (66.49); H, 6.66 (6.64). B. Preparation of Pd and Pt Complexes. The Pd and Pt complexes were prepared by dissolving 0.15 g of the appropriate (PhCN)2MC12 in minimum amount of dry warm benzene and a slight excess of ferrocenylsulfide or selenide ligand in an approximate 1:1.1 molar ratio was added. The reaction mixture was stirred at room temperature for 12 h in the case of Pd complexes or five days in the case of Pt complexes. The resulting precipitates were filtered, washed with benzene then with petrolium ether, and recrystallized from CH2C12/hexane. 28 (S,R)-1-(l-Dimethylaminoethyl)-2-methy1thioferrocene Palladium(II)dichloride (46, R = Me). The general procedure was followed by use of amine thioether 41. The product was obtained as dark purple crystals: yield 74%; mp 162-1640c (dec). 1H NMR 5 ppm (J in Hz), 4.49, 4.36 (m, C5H3); 4.21 (s, Cp); 3.84 (q, gflMe, 6.7); 2.29 (s, NMeZ); 2.67 (s, SMe); 1.51 (d, cnge, 6.7). IR (Nujol, CsI), 304, 335 (metal-S, metal-Cl stretch); 466 (metal-N stretch). MS m/e (relative intensity), 303 (M+-PdC12); 258 (18.43, M+-ch12-HN(CH3)2); 243 (10.56, M+-HN(CH3)2-Me); 121 (28.40, CpFe); 56 (24.55, Fe); 44 (100.00, N(CH3)2). Elemental Analysis for C15H21FeNSPdC12 (calcd.): C, 36.65 (37.49); H, 4.42 (4.40). (S,R)-1-(l-Dimethylaminoethyl)-2-ethylthioferrocene Palladium(II)dichloride (47, R = Et). The general procedure was followed by use of amine thioether 42. The product was obtained as purple crystals: yield 82%; mp 154-1560c (dec). 1H NMR 8 ppm (J in Hz), 4.51, 4.35 (m, C5H3); 4.20 (s, Cp); 3.85 (q! EfiMe, 6.7); 3.57 (m, SCH2); 2.22 (s, NMez); 1.69 (t, CHZ-gH3, 7.4); 1.50 (d, CHMe, 6.7). 29 IR (Nujol, CsI), 305, 330 (metal-S, metal-Cl stretch); 470 (metal-N stretch). MS m/e (relative intenisty) 272 (15.77, M+-Pdc12- HN(CH3)2); 243 (13.95, M+-Pdc12-HN(CH3)2-Et); 121 (32.14, CpFe); 56 (26.08, Fe); 44 (100.00, N(CH3)2). Elemental Analysis for C16H23FeNSPdCl2 (calcd.): C, 39.14 (38.86); H, 4.66 (4.69). (S,R)-1—(l-Dimethylaminoethyl)-2-n-propylthioferrocene Palladium(II)dichloride (48, R = n-Pr). The general procedure was followed by use of amine thioether 43. The product was obtained as brown crystals: yield 69%; mp 162-1640c (dec). 1H NMR 5 ppm (J in Hz), 4.70, 435 (m, C5H3); 4.19 (s, Cp); 3.84 (q, ggme, 6.7); 3.54 (m, SCHZ); 2.28 (s, NMe2); 2.17 (m, scazggz); 1.53 (d, Cng, 6.7); 1.15 (t, CHZCH3, 7.3). IR (Nujol, C81), 307, 330 (metal-S, metal-Cl stretch); 465 (metal-N stretch). ms m/e (relative intensity), 331 (M+- PdClZ); 286 (13.71, M+—PdC12-HN(CH3)2); 243 (11.51, M+-Pdc12-HN(CH3)2)-n—Pr); 121 (25.54, CpFe); 56 (17.26, Fe); 44 (66.50, N(CH3)2). Elemental Analysis for C17H25FeNSPdCl2 (calcd.): C, 40.04 (40.14); H, 4.87 (4.95). 30 (S,R)-1-(l-Dimethylaminoethyl-Z-isopentylthioferrocene Palladium(II)dichloride (49, R = i-Pent). The general procedure was followed by use of amine thioether 44. The product was obtained as deep purple crystals: yield 64%; mp 147-1490C (dec). 1H NMR 8 ppm (J in Hz), 4.47, 4.37 (m, C5H3); 4.19 (s, Cp); 3.82 (q, gHMe, 6.7); 3.67, 3.06 (m, SCHZ); 2.28 (s, NMGZ); 2.07 (m, SCHZEEZ); 1.83 (m, 2111482); 1.50 (d, CHE/IE, 6.7); 1.01 (d, CHHEZ, 6.3). IR (Nujol, C31), 303, 327 (metal-S, metal—Cl stretch); 463 (metal—N stretch). MS m/e (relative intensity); 314 (20.14, M+-PdC12- HN(CH3)2; 243 (14.49, M+-PdC12-HN(CH3)2-i-Pent); 121 (31.10, CpFe); 56 (27.56, Fe); 44 (100.00, N(CH3)2). Elemental Analysis for C19H29FeNSPdC12 (calcd.): C, 41.76 (42.52); H, 5.37 (5.45). (S,R)-1-(1-Dimethy1aminoethy1-2-benzylthioferrocene Palladium(II)dichloride (50, R = 82). The general procedure was followed by use of amine thioether 45. The product was obtained as deep purple crystals: yield 63%; mp 147—1480C (dec). 1H NMR 5 ppm (J in Hz), 7 34-7.59 (m, Ph); 4.54, 4.31 (m, C5H3); 4.10 (d, SCH, 14.6); 3.73 (s, Cp); 3.78 (q, gHMe, 31 6.6); 3.22 (d, SCH, 14.6); 2.26 (s, NMeZ); 1.44 (d, CHHe, 6.3). IR (Nujol, C31), 310, 335 (metal- S, metal-Cl stretch); 470 (metal—N stretch). MS m/e (relative intensity), 334 (26.80, M+-PdC12- HN(CH3)2); 243 (55.04, M+-PdCl-HN(CH2)2-Bz); 121 (76.67, CpFe); 91 (82.93, PhCHZ); 56 (37.59, Fe); 44 (100.00, N(CH3)2). Elemental Analysis for C21H25FeNSPdC12 (calcd.): C, 45.80 (45.31); H, 4.58 (4.53). (S,R)-1-(1-Dimethy1aminoethyl-2-methy1thioferrocene Platinum(II)dichloride (51, R = Me). The general procedure was followed by use of amine thioether 41. The product was collected as yellow crystals: yield 61%; mp 180-1810C (dec). 1H NMR 8 ppm (J in Hz), 4.47, 4.31 (m, C5H3); 4.20 (s, Cp); 4.18 (q. gHMe, 6.7); 3.34, 2.45 (s, NMeZ); 2.71 (s, SCH3); 1.57 (d, CHHe, 6.7). IR (Nujol, CsI), 310, 338 (metal-S, metal—Cl stretch); 472 (metal-N stretch). MS m/e (relative intensity), 258 (11.79, M+-PtClZ- HN(CH3)2); 243 (1.24, M+-PtC12-HN(CH3)2)-Me); 121 (23.32, CpFe); 66 (64.27, Cp + H+); 44 (58.51, N(CH3)2). 32 Elemental Analysis for C15H21FeNSPtC12 (calcd.): C, 31.95 (31.65); H, 3.77 (3.72). (S,R)-1-(1—Dimethy1aminoethyl-2-ethylthioferrocene Platinum(II)dichloride (52, R = Et). The general procedure was followed by use of amine thioether 42. The product was collected as yellow crystals: yield 63%; mp 180-1820c (dec). 1H NMR 8 ppm (J in Hz), 4.51, 4.38 (m, C5H3); 4.19 (s, cp); 4.12 (q, gHMe, 6.8); 3.67, 3.18 (m, SCH2); 3.32, 2.45 (s, NMeZ); 1.68 (t, SCH29H3, 7.3); 1.53 (d, CHMe, 6.8). IR (Nujol, C31), 305, 330 (metal—S, metal—Cl stretch); 469 (metal-N stretch). MS m/e (relative intensity), 272 (1.68, M+-PtC12- HN(CH3)2); 243 (1.79, M+-PtC12-HN(CH3)2—Et); 121 (4.74, CpFe); 66 (8.83, Cp + H+); 44 (100.00, N(CH3)2). Elemental Analysis for C16H23FeNSPtC12 (calcd.): C, 33.51 (32.95); H; 3.95 (3.97). (S,R)-1-(l-Dimethylaminoethyl-Z-n-propy1thioferrocene Platinum(II)dichloride (53, R = n-Pr). The general procedure was followed by use of amine thioether 43. The product was collected as yellow crystals: yield 56%; mp 174-1750c (dec). 33 1H NMR 8 ppm (J in Hz), 4.47, 4.34 (m, C5H3); 4.19 (s, Cp); 4.14 (q. ggMe, 6.5); 3.67, 3.09 (m, SCHZ); 3.33, 2.45 (s, NMeZ); 2.22, 2.01 (m, SCHZCHZ); 1.56 (d, CHMe, 6.5); 1.50 (t, CHZCH3, 7.2). IR (Nujol, C31), 292, 328 (metal-S, metal-Cl stretch); 462 (metal-N stretch). MS m/e (relative intensity), 286 (1.37, M+-PtC12- HN(CH3)2); 243 (1.50, M+-PtC12-HN(CH3)2—n—pr); 121 (5.18, CpFe); 66 (15.17, Cp + H+); 44 (100.00, N(CH3)2). Elemental Analysis for C17H25FeNSPtC12 (calcd.): C, 34.87 (34.19); H, 4.28 (4.22). (S,R)-1-(1-Dimethylaminoethyl-2-isopropylthioferrocene Platinum(II)dichloride (54, R = i-Pr). The general procedure was followed by use of (S,R)-1- (dimethylaminoethyl-2-isopropylthioferrocene which was prepared according to the reported procedure.88 The product was collected as yellow crystals: yield 59%; mp 180-1820C (dec). 1H NMR 8 ppm (J in Hz), 4.30, 4.41 (m, C5H3); 4.26 (s, Cp); 4.04 (q, gHMe, 6.1); 3.57 (m, SCH); 3.34, 2.45 (s, NMeZ); 1.76 (d, CHMeZ, 15.5); 1.56 (d, CHMe, 6.1). IR (Nujol, CsI), 305, 338 (metal-S, metal-Cl stretch); 471 (metal-N stretch). 34 MS m/e (relative intensity), 286 (1.92, M+-Ptc12— HN(CH3)2); 243 (1.71, M+—PtC12-HN(CH3)2-i-Pr); 121 (6.01, CpFe); 66 (14.46, Cp + H+); 44 (100.00, N(CH3)2). Elemental Analysis for C17H25FeNSPtC12 (calcd.): C, 34.41 (34.19); H, 4.19 (4.22). (S,R)-1-(l-Dimethylaminoethyl-Z-methylse1enoferrocene Platinum(II)dichloride (55, R = Me). The general procedure was followed by use of (S,R)-1-(1- dimethylaminoethyl-2-methylselenoferrocene which was prepared according to the reported procedure.88 The product was collected as yellow crystals: yield 62%; mp 185-1870C (dec). 1H NMR 5 ppm (J in Hz), 4.46, 4.35 (m, C5H3); 4.20 (s, Cp); 4.14 (q; EflMe, 6.7); 3.36, 2.44 (s, NMe2); 2.68 (s, SCH3); 1.55 (d, CHMe, 6.7). IR (Nujol, CsI), 305, 330 (metal-S, metal-C1 stretch); 461 (metal-N stretch). MS m/e (relative intensity), 227 (7.56, M+-PtC12-N(CH3)2- SGCHB-CH3); 57 (56.3, CHN(CH3)2; 44 (23.53, N(CH3)2. Elemental Analysis for C15H21FeNSePtCl2 (calcd.): C, 29.42 (29.24); H, 3.38 (3.44). 35 C. Preparation of Ni Complexes. Ni complexes of amine thioether and selenoether of types (S,R)'(ns-C5H5)Fe(nS-C5H3-l-CH(Me)NMe2-2-SR)(NiClz) where R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu, i-Pent, 82, Ph and 4-Tolyl (56-65), (S,R)-(n5-C5H4-SR)Fe(nS-C5H3-l-CH(Me)NMe2-2- SR)(NiC12) where R = Me, i-Pr, t-Bu and 4-Tolyl (66-69), and (S,R)'(ns-CsH3-l-CH(Me)NMe2-2-SeR1)Fe(ns-C5H4-R2)(NiClZ) where R1 = Me, R2 = H (70), R1 = Me, R2 = SeMe (71) and R1 = ClC6H4, R2 = H (72) have been prepared, in situ, in ether solution and used directly as catalysts in Grignard cross- coupling reactions as described below in detail D. Grignard Cross-Coupling Reactions by Using Ni Catalysts. A 64 mg (0.049 mmol) of NiC12 and 0.049 mmol of the appropriate ligand were placed in a lOO-mL round-bottomed Schlenk flask. The flask was evacuated and filled with argon several times then 10 mL of freshly dried ether was added and stirred for 2 h. The solution was cooled to -78OC, then 1.41 g (10.0 mmol) of 1-phenylethyl-chloride 73 dissolved in 10 mL dry ether was added via syringe and the reaction mixture was stirred for 2 h at room temperature. After cooling to -780C, 10 mL of 2M solution of allylmagnesium chloride 74 in THF was added Via syringe dropwise, then the reaction mixture was stirred at room temperature for 36 h. After hydrolyzing with 10 mL 10% HCl, the organic layer and ether extracts from the aqueous layer were combined, washed 36 with saturated NaHCO3 solution then water, dried over Na2804 and evaporated. The product was chromatographed on a silica gel column to give 4-phenyl-1-pentene 75 (92-97%). E. Grignard Cross-Coupling Reactions by Using Pd and Pt Catalysts. A 0.049 mmol of the appropriate catalyst was placed in a 100-ml round-bottomed Schlenk flash then it was evacuated and filled with dry argon several times. After being cooled to -780C, 1.419 (10.0 mmol) 1-phenylethyl chloride 73 in 20 mL dry ether was added via syringe then stirred for 2 h at room temperature. The reaction vessel was charged with 10 mL allylmagnesium chloride 74 2 M solution in THF (20 mmol) Via syringe at -78OC. The reaction mixture was stirred at room temperature for 36 h then hydrolyzed with 10 mL 10% HCl and worked up as described above. Oxidation of 4-phenyl-l-pentene to methyl-3-phenylbutyrate 76. 89 was used as follows: A 0.906 g The reported procedure (6.2 mmol) of 4-phenyl-1—pentene 75 was disolved in 160 mL t-butyl alchol; then a solution of 2.48 g (18.0 mmol) K2CO3 in 120 mL of water and a solution of 10.26 g (48.0 mmol) sodium periodate and 1.26 g (8.0 mmol) KMnO4 in 120 mL water were added. The solution was adjusted to PH 8.5 with 2N aqueous NaOH and stirred overnight. t-Butyl alcohol was evaporated under reduced pressure; then the PH of the 37 aqueous solution was adjusted to 2.5 with concentrated HCl. Sodium bisulfite was added slowly until the solution become off-white. The aqueous solution was extracted twice with ether; then extracts were combined, washed, dried over anhydrous K2C03 and evaporated. A solution of the resulted acid (0.590 g, 3.5 mmol) and p-toluensulfonic acid (80 mg) in 20 mL of methanol was refluxed for 3 h, then the solvent was removed and the residue was taken up in ether. The ether solution was washed with 10% aqueous NaOH, dried over anhydrous Na2804 and evaporated. The residue was distilled at 110-1300C (2 mm) to give methyl-B-phenylbutyrate 76 (75- 85%). A 90 mg of the chiral shift reagent, tris(d,d- dicampholylmethanato)europium(III), Eu(dcm)3, was placed in NMR tube under argon condition and 0.15 mL 1 M solution of methyl-3-phenylbutyrate 76 in CDCl3 was added. The solution was diluted to 0.3 mL with CDCl3 to give 0.27 M in Eu(dcm)3 and 0.5 M in 76. Argon was bubbled in the solution for one minute to get ride of the oxygen then the NMR tube was evacuated and seald. The methyl ester protons of the two diastereomers give two singlets, which their ratio gives direct measure to the enantiomeric excess. F. Selective Hydrogenation of Conjugated Dienes to Monoenes. The palladium or platinum catalyst (1x10.5 mol), 4.5 mL acetone (3.5 mL acetone and 1 mL H20 in the case of platinum catalysts) and the appropriate substrate (3.725 x 10'3 mol) were added to a 100-mL pressure bottle equipped with 38 a pressure gauge and a stirring bar. The bottle was evacuated and filled with H2 several times, then fixed at a determined pressure. The uptake of the hydrogen was observed and if there was an induction time, it was recorded. The product was distilled from the catalyst and analyzed by using GC and 1H NMR. For the hydrogenation of cyclooctadiene, cyclohexadiene or 2,3-dimethy1—l,3-butadiene double of these amounts were used. The initial hydrogen pressure was fixed at 104 Psi for the hydrogenation of cyclooctadiene or cyclohexadiene and 81 Psi for other substrates unless the hydrogen pressure was under investigation. For palladium catalysts the solvent was acetone unless the solvent effect was studied. G. Selective Hydrogenation of Carbon-Carbon Double Bond Conjugated to Different Functional Groups. The same procedure was used with substrates having carbon-carbon double bonds conjugated to aldehyde, ketone, acid, ester, amide, lactone and nitrile. All liquids substrates were freshly distilled before hydrogenation. 39 RESULTS AND DISCUSSION Since the early 19703, spectacular progress has been made in the field of asymmetric catalysis by using homogeneous catalysts based on transition metal complexes modified by chiral ligands and became an important class in asymmetric synthesis. Chiral phosphine ligands proved to have good catalytic properties when they are coordinated to different transition metals. Among those phosphines, chiral ferrocenylphosphines have been superior for structural modification and can readily be made by introduction of a desired functional group on the side chain according to the reaction type. However, these ligands are oxygen sensitive and can undergo oxidation by air. This severe limitation induced us to prepare various new series of ferrocenyl- sulfides and their palladium and platinum complexes.90_ 96'129'131 These catalysts proved to be efficient in asymmetric Grignard cross-coupling reactions and selective hydrogenation of cyclooctadiene and cyclohexadiene to cyclooctene and cyclohexene respectively. Therefore, we decided to prepare new series of nickel complexes of chiral ferrocenylamine sulfides and selenides. Some of their new palladium and platinum analogs have also been prepared for comparison study. Scheme 8 shows various structure modification in the synthesis of ferrocenylamine catalysts, which have been made in this work to include the following features: (a) changing 40 the electrophiles attached to the cyclopentadienyl ring to include sulfur and selenium. (b) By using different alkyl groups on the sulfur or selenium atoms i.e. Me, Et, n-Pr, i- Pr, n-Bu, t-Bu, i-Pent, 82, Ph, p-Tolyl, and 4-ClPh which poses different steric bulkiness around the metal. (c) Introducing another electrophile to the second cyclopentadienyl ring. (d) Changing the metal to include nickel, palladium, and platinum. M:Ni,Pd,Pt E=S,5e R1=Me,Et,n—Pr,i—Pr,n-Bu,t-Bu,i—Pent,BZ,Ph,4-Tolyl,4—CIPh R22H, 591,569.] Scneme 8: Various Structure Modification of Ferrocenylamine Catalysts. Since choosing chiral catalysts is still mainly empirical task, introducing structurally different catalysts helps understanding the factors that affect the catalytic activity Iii' 41 and the enantioselectivity of such catalysts. In general, these catalysts are interesting not only because they are air stable and posses both center and planar chirality but also because of the high catalytic activity and selectivity achieved in both hydrogenation and asymmetric cross-coupling reactions. A. Synthesis of Chiral Ferrocenylamine Catalysts. 1. Synthesis of Chiral Ferrocenylamine Ligands. i. Preparation. The starting material, (S)-N,N-dimethyl—l-ferrocenyl- ethylamine (5)-22, was prepared and resolved by using (R)- (+)-tartaric acid as described by Ugi.31 Lithiation of (S)- 22 is stereoselective to give 96% of the (S)-(S)-23. It is due to the stabilization resulted from the coordination of the neighboring amino group with the lithium atom. The lithiated product reacts with different alkyldisulfides to give the ferrocenylamine thioethers (S)-(R)-41-45 as shown in Scheme 9. The (S) configuration refers to the chirality of the asymmetric carbon on the side chain while the (R) configuration refers to the planer chirality. The yields are fairly high (51%-76%) and two products (41,43) were obtained as brown crystals after recrystalization from CH2C12-hexane. 88 and disulfides96 The other mono— or selenides ligands used in this work were prepared according to the reported procedures. 42 p—BuLi C§3-C§3-23 R252 MeH 4," NMe2 Fe SR © C§3-CBD-41-45 R:Me,Et,rvi%')i—Pent,BZ (41—45) Scheme 9: Synthesis of Ferrocenylamine Sulfide Ligands. 43 ii. 13 NMR. The 250 1H NMR data for the chiral ferrocenylamine thioethers 41-45 are tabulated in table 1; representative spectrum is shown in figure 1 for compound 44 (R = i-Pent). Protons of the unsubstituted cyclopentadinyl ring appear as a singlet due to the free rotation around the Fe-Cp axis in ferrocenesg7; the rotation barrier is only about one-third of that of the two methyl groups in ethane.98 Assignment of the substituted ring protons is not made because of the ambiguous shielding or deshielding effect of the substitunets. The two methyl protons of NMe2 show up also as a singlet because the inversion of the pyramidal N is faster than the NMR time scale at room temperature. The SCH2 protons in compounds 42-44 (R = Et, n-Pr, i—Pent) are diastereotopic and their signal shows up as multiplet because of the additional splitting by the neighboring protons. The PhCH2 protons should appear as two doublets however, they are deshielded by the neighboring phenyl group to 3.95 ppm and overlapped with CHMe quartet. The two methyl groups of the isopenytyl group (compound 44, R = i—Pent) are also diastereotopic and show up as two separate doublets (J = 0.26 Hz) at 0.85, 0.83 ppm. iii. 13c NMR. The data obtained from 13C NMR of ferrocenylamine thioethers 41-45 are given in table 2. Although assignments 44 N: 5 E338 @5338 m 542 585 8% 3.835.— 8553 5m: .586 83. we? smegma .83 521 5 .3 58m 8 _ .N 3.32.... 6.8.88... 5 . .v .5 .3. $3 cease: 85.85 55.. 55m. 88 8.983 8.3 £3 59... .585 more 5.52 8.98.0 585 8..“ 8.98m.— 8933 5m; .533. 8...... ewe? ...Rm 3 I... 8858.— maécmam 5m: .58... 68.". 82:4 an. m > n 8 mm 822 fire dleo mzmo do E55858 .a vs 59.58 5355.8 use 5-3 8:8: .2 5% «=22 seed ”F are» 45 .xucwdiw E . l e. as? my vv oczoaeou Mo Esuuowam mzz ma ”H ousmfim _LLL m &.r @.mw Q.w 8.x- 46 CNNNN— 88.8. 28.8. 8. .03 8. s. 8.9. :8 8.8 82 8.8.8.8 8.2 8.8 8.8 “va8 2.8 8.8 8.8 8.8 8.8 2.2 8.8 82 8.8.8.8 :2 2.8 8.8 58.53 2.2 8.8 8.8 2.8 8.2 8.8 82 8.8.8.8 2.2 2.8 8.8 5.58 8.2 N _. 8 3.8 8.2. 8.8 8.2 8.8.2.8 3 .2 8.8 8.8 8:8 8.9 8.8 8. 2 8.8 8.2 3.8.2 .8 3 .2 :8 8.8 82:”. rd m a m 8 g mm 8.22 fire ..le do 80 .80 no No P0 88: . on - 2658 E Wm .8ch .2 San E22 09 83:8 c065 ”N .2me 47 were tentative, ambiguity was solved by getting proton coupling 13C NMR spectra of all compounds. Typical proton decoupling and proton coupling 13C NMR spectra of ferrocenylamine thioethers 41,44,45 (R = Me,i—Pent,Bz) are presented in figures 2-7 respectively; spectra of other compounds are showed in the appendix. The Cp carbons of the unsubstituted ring gave only one signal at about 70 ppm because of the free rotation around the Fe-Cp axis. It also shows the two methyl of NMe2 as a singlet at about 40 ppm because of the fast inversion of the pyramidal nitrogen atom. These compounds are chiral and thus the two methyl of the isopentyl group of compound 44 are diastereotopic and showed up as two singlets at about 22 ppm. iv. Infrared (IR) Spectra. The infrared data of ferrocenylamine sulfides 41-45 listed in table 3 are tentatively assigned by comparison with the 99 vibrational spectra of ferrocene,24 dimethylferrocene, and other ferrocenylamine sulfides reported previously.92'94 All the spectra have common features at certain frequencies. As reported,24 the asymmetric ring breathing bands at about 1000 and 1100 cm"1 are important features of IR spectra of ferrocene derivatives with unsubstituted rings. Other common frequencies for all compounds as shown in table 3 are asymmetric ring-Fe stretch ( 472 cm'l), asymmetric ring tilt (520-505, 559-541 cm"l), ring-H bend perpendicular to ring 48 .Amz u my av UCDOQEOU mo Ezuuommm mzz UmH "N wusmam 0 ON 0v cm 0 .._______.___EE. _..__.___.____.___.___.__.._E..._______._._______..._..__ ,l Lt b?» {III} i b }y E L L L! r L} t 1 1 1‘1 ll 4 _ — ll ‘ 14 1 14 11‘ 41 I m cow 9: «m: com 0mm om H o v — Eng EE.§:E PEEEL+EEL EtELE:t.L EFF: 49 .Amz n my av ocsodeoo mo Esuuommm mzz UmH mafiadsoo cououm "m musmflm om ow om om on om om cod ——P—p—thr—p-hP—P-bp—bphp—ppPh—h-p.—rhbp—pppb—-bnh—nbpb—nh-P—prn—p-h~_-PP—-pP—P>»-—»E {rib-I} 9’ F’h PL! rub b. ’ DD lb) 95 r ... D}? bl It, 8 bib" 5 LIFE 11 {j ‘11 1 1 {41 ll‘lil 11 J‘1#JL 11:1 1111 lc‘ld ‘ ‘ 111 ‘11! 11 50 om ow ow .Aucmmsw ow mv vv UGDOQEOU mo Esuuommm mzz UMH "v musmflm oofi omfi ow“ ow“ om“ com _ _ _ . _ _ _ _ _ _ _ _ 0mm 51 .Aucmmuw u me vv UCDOQEoU mo Esuuooam mzz UmH ocfladsoo cououm "m musmflh cm on 0? on ow L_-hh-pbbb_-PbPP-pp#—pp-rP—P-PP—DP-p—[h-P 2 8 8 2: o: D—rrpbp—DPbb_thhPPrbh_-bP—bphb— DPb-b-Pbb—b-bb—bbbP—h 3.3}: 52 .ANm u my mt UCDOQEOU mo Esuuoodm mzz UmH um wusmflm 0 ON ow om om oo« om“ ow“ on: om: com 0mm :—:-::: -:_p:-———:—:~: —P»»-:»—:~»~>-.b—:p:»:_—.p::-p——::::—::-b:_:-:::_»—:P:-—:-—::———_::—:_::::_—_»_-::—:_:b:_—:p:—:b—_ppppb:—r-E—pP—p—p-p-h-anb:—--._-:b=—:——::_—:—:::-— Ili>rb£ D IDD|||*’ ." "| ‘ .P"l.l h uh InnI . y I. D ' P ’ } Dthubil’ DDI’ID F, by. i fl 1 11‘ fil .- 111 I‘ll: 1 “ fi1‘1‘111 1‘ 1 ‘14 ‘1111 ‘44 1 1‘1 ‘1}! 14 11 1‘41 Ill‘ 53 om i on ov . «um om my mv UCSOQEOU mo Esuuomam mzz omH mcflamsoo cououm ”b wusmflm cm on on om 00a 0"" om" om« ov« on“ ii until 8 - a , - - 54 omm mop P m2: ommm at. O8 o8 82 82 82 88 a. N8 8: 22 88 8... 88 88 89 8: 82 88 3. N8 2 : 22 88 o8 88 88 29 82 82 88 a. 88 8: 22 88 88 88 08 ms— 82 82 28 2. o8 8: 22 88 E. 88 O8 22 2 : 82 88 z. 8: 2 81.22888 8: 2 8:98 @5585 .8 8.8.8 .82 88. 1-88 83 1-88 8.: .82.- It... 2. .-o 88. 1-0 I8 z-o 88: .83.. 888 .2 80 8.8. 8 82 55 (820 cm'l), ring-H bend parallel to ring ( 940, 981 cm_l), asymmetric ring breathing ( 1010, 1103 cm'l), C-N stretch ( 1200 cm‘l), alkyl C-H bend ( 1260, 1274 cm‘l), and alkyl C-H stretch ( 2780, 2820 cm'l), In addition, compound 45 (R = 82) shows the out-of-plane bending of the phenyl ring C—H bonds at 910 cm"1 and the C-C stretching within the phenyl 1 ring at 1610 cm” ; the infrared spectrum of this compound is presented in figure 8. v. Mass Spectra. The mass spectra of the thioethers 41-45 are explained in the experimental section. The molecular ion peak is present in all spectra. Other common fragments are M+-HN(CH3)2-R), M+-HN(CH3)2, CpFe+, Fe+, and HN(CH3)2 which is usually the base peak. The mass spectrum of compound 43 (R = n—Pr) is shown in figure 9; the others are shown in the appendix. 2. Synthesis of Palladium and Platinum Complexes. i. Preparation. The procedure was similar to that used for preparing other ferrocenylamine complexes reported previously;92’94 however, shorter times were used, i.e. 12 h for palladium or four days for platinum complexes. The prepared palladium and platinum catalysts are presented in scheme 10. The procedure includes dissolving the bis(benzonitrile) adduct of palladium or platinum chloride in the minimum amount of warm 56 00.00V 00.000 0.00Nd 0.000d adIEUU 0.000N 0.00VN 0.000N 0.00Nm 0.000m 0.000? .Anm n my mv vasoQEoo mo Esuuomam mH "m ousmfim LODEJCO>03 -..w- 000'08 000'09 000'07 000'08 0000'0 oouaathauaulx 00'00? 00°03‘ 57 mtg mvm 0mm Nam .Aumu: com mm” mm" m: mm" on NB v9 a IV 0 a 03 5 mm Nu mm 3. av mv ocsomeoo mo m2 um musmfim m\z [0.0m I 0.00— 58 Me H ’4. We2 Fe E“,MCIZ C83-CEj-Ligands Scneme 10: Synthesis Complexes. l (PnCNj2MCl2 “ p Benzene C§)-CBj—Pd or Pt catalysts szd: EzS; R:Me,Et,n-Pr)i—Pent,Bz (46-503 szt: E28 RzMe,Et,n—Pr,i—Pr {51-54) szt: E=Se RzMe (55) of Ferrocenylamine Palladium And Platinum 59 dry benzene then the appropriate ligand was added. The reaction mixture was stirred for the desired time then the crude suspension (product) was filtered, washed with petroleum ether, and recrystalized from CHZClZ/Hexane. The obtained catalysts were stable for months without detected oxidation or decrease in their catalytic activity. The palladium catalysts were either purple or brown and soluble in methylene chloride and chloroform while the platinum catalysts were yellow and less soluble. The melting points and the analytical data of the ligands and the metal complexes are collected in table 4. ii. 13 NMR. The 250 1H NMR data for palladium 46-50 and platinum 51-55 complexes are summarized in tables 5,6 respectively. The most striking difference in the 1H NMR spectra of these complexes relative to their corresponding free ligands is the appearance of two separate singlets for the two diastereotopic methyl groups of NMeZ. That is due to the formation of six-membered ring that locks the inversion of the pyramidal N. Comparison of the spectra of the palladium complexes with those of their platinum analogs indicates that the platinum has a more inductive effect in desielding the two methyl protons of NMe2(2.45, 3.34 ppm) more than the palladium complexes (2.29, 3.19 ppm) as shown in the 1H NMR spectra of the palladium 46 and platinum 51 complexes, where R = Me in both, as presented in figures 10 and 11 60 Table 4: Yields, Melting Points, And Analytical Data of The New Ligands And Palladium And Platinum Complexes. Analytical Data Compound Xield Melting (found(calc.)(%) m g a 41 76 64—66 59.79(59.41) 7.01(6.98) 42 51 oil 60.89(60.57) 7.27(7.31) 43 68 32.33 61.68(6l.63) 7.68(7.61) 44 65 oil 63.91(63.51) 8.l3(8.13) 45 72 oil 66.59(66.49) 6.66(6.64) 56 74 162—164 36.65(37.49) 4.42(4.40) 47 82 154-156 39.14(38.86) 4.66(4.69) 48 69 162-164 40.04(40.14) 4.87(4.95) 49 64 147-149 41.76(42.52) 5.37(5.45) 50 63 147-148 45.80(45.31) 4.58(4.53) 51 61 180-181 31.95(31.65) 3.77(3.72) 52 63 180-182 33.51(32.95) 3.95(3.97) 53 56 174-175 34.87(34.19) 4.28(4.22) 54 59 180-182 34.41(34.19) 4.19(4.22) 55 62 185-187 29.42(29.24) 3.38(3.44) 61 NI E =6.ch 959.8 m 8.3983 8; 588.58 8.3688 88.8 8.932..— 8933 684.588 .888 898 58.8 .8; 8.923 58.— 588 E88 $8.8 8.98m.— 8.9c~m.m 588.58.... 8:. €8.92. E28 58.8 8.8 8.83: 52.8 53.8 88.8 8.983 8.9388 53.8.60: 83. ESQ. am; 8; 38:8.— Ekmd «.888 8.989. 8.9$m.m 688.55.". 88.2. 398. 83 80.8 88.8 8.923 «8.9988 58.455: 33. 85:8. .8 w 8 a 5 mm 8822 filo 823 ammo no 2983858 .879 99.28 E3828 ucm 8-9 8:89. .2 28 822 :29; ”m 298 62 NI c_ E388 9:98 a mm .m u m a SE :53 $3 $3 8983 8,9¢3,v 63.". 83. mm 83.“. E3. 8.398: :83 39m 2989— 2.995.". :53. £3 E 58a 58d $3 Ev? 8.98m.— E-.~ E89,” mm: 3.92%; 8.932. :81. mm: mm .52.. mmvu Em: 38x8.— ESd $3 8983 8.953. 2:3. 33 Nm 83 ES». £2 3.3 8.923 9893—... :83. 83 S > a a mum N222 fire mle mxmo 8 2:38 .82“: $2.28 5:563 can 523:8 § 9% E22 865 no 033 .Amz u m9 wv meQEoo EDfivaamm mo Esuuommm mzz ma ”0H wusmflm v." o.« m." od m.m v.m ©.N m.N o.m m.m v.m w.m. oh o.v N.V v.v w.v 63 . 82 av Hm meQEou Escflumam mo Esuuowmm mzz mH "Ha musmflm 65 respectively; spectra of other complexes are collected in the appendix. Another striking feature of 1H NMR spectra of the platinum complexes is the 195Pt (I = 1/2) coupling with protons on a-carbons to N and S. The diastereotopic nature of the SCH2 protons increases their splitting pattern complexity and causes difficulty to determine their coupling constant with 195Pt; however, the coupling constant of 195Pt with the neighboring methyl protons are listed in table 7 which is comparable with the results reported before.100 The coupling consistent of 195Pt with NMe2 protons is 29 Hz, while that of 195Pt with SMe and SeMe protons are 51.9 and 45.7 Hz respectively. These values are constant with the reported J values for platinum complexes containing PMe3 or other analog ligands which are between 15-57 £12.10l 195Pt has a natural abundance of 33% and has been found to be roughly the same relative intensity of the two setilite around the singlet of the aminomethyl protons. iii. Infrared (IR) Spectra. The most important bands in the IR spectra of palladium and platinum complexes are the metal-Cl, metal-N, and metal- E (where E = S or Se) stretching bands in the low frequency region. These frequencies are listed in table 8 and representative spectra of compounds 47 (M = Pd; R = Et) and 52 (M = Pt; R = Et) are shown in figures 12 and 13 respectively, other spectra can be found in the appendix. The metal—Cl and metal—E stretching bands are so close that 66 Table 7: Coupling Constants (Hz) of 195Pt with The Entry Neighboring Protons. Catalyst 51 52 53 54 55 NCH3(§,PPM) 28. 30. 29. 29. 30 9(2. 4(2. 6(2 6(2 .2(2 45) 45) .45) .45) .44) NCH3(§,PPM) 28 29. 28 29 28 .9(3. 5(3. .5(3. .7(3. .4(3. 34) 32) 33) 34) 36) SCH3(5,PPM) 51.9(2.7l) 45.7(2.68) 67 Table 8: Metal-S,-Se,-Cl, and-N Stretching Modes of Palladium (46-50) and Platinum (51-55) Complexes.a a frequency in Cm" b E Catalyst im-Eb, vM—Cl VM-N 46 304m, 3355 466m 47 305w, 3303 4703 48 307m, 3305 465m 49 303m, 327m 463m 50 310$, 335$ 470m 51 310m, 338m 472m 52 3053, 3308 4698 53 2923, 3283 4623 54 3053, 338m 4713 55 3053, 330$ 461$ 56 3055, 3303 4615 1 00.00? P 68 00.000 0.00N« 0.000d 0.000N 0.00VN 0.000N 0.00Nm 0.000m 0.000? [r L b PP L b L b my bv onQEoo Esflomaamm mo Esuuommm mH "NH ousmwm Loneaco>oz d # 4 d 000'08 000°09 OOO'OP 000'08 OOOO'O eoueqthaueulx OO'OOI 00°08? . 00.00? P) 69 ¢ .Aum n me an meQEOU escaumam mo Esauomam mH "ma magmam Adi-SUV LIDEJCO>03 14 00.00% 0.000% 0.000% 0.000% 0.00?W 0.000% 0.000% 0.000% 0.000? .9 l. + i. .9. a. 000'08 000'09 000'07 000'08 0000'0 eaucqqtmauaqlx 00°00? 00'08? 70 it is often difficult to distinguish them; thus, the tentative assignment was metal-Cl and/or metal-E stretch for 305 and 330 cm“1 bands and metal-N stretch for 365 cm-1 band. These assignments are around the literature values for the Pd-Cl,102-105 Pd_s'102,106-108 Pd-N,103 Pt‘Cl,105 Pt- 3,107,109,110 and Pt-Nllo stretching bands. iv. Mass Spectra. The molecular ion peak is always absent in the mass spectra of palladium and platinum complexes; however, peaks represent M+-MC12HN(CH3)2, M+-MC12-HN(CH3)2—R, CpFe+, Fe+ fragments are present. The base peak is usually for N(CH3)2 fragment as was for the organic ligands. The mass spectra of each individual complex was discussed in detail in the experimental part. Mass spectrum of compound 50 (M = Pd, R = 82) is presented in figure 14. 3. Synthesis of Nickel Complexes. Nickel complexes were prepared in situ by stirring the appropriate ligand and anhydrous NiC12 in dry ether for two hours under predried argon condition (scheme 11). Attempt to isolate the product failed and gave dark green insoluble material even if handled under oxygen free condition. This is consistent with most procedures used for preparing similar NiClZ complexes which were also prepared in situ.35'59 All nickel complexes prepared are used directly as catalysts for Grignard cross—coupling reactions as 71 .le n my on xmaceoo anaemafimm co m: “ea magmas see emm mom emu sea owl ee_ a. or: u —--.b-r-—- .p..u.—-p-p.p-— :1 8m mmm . mm: _ new ee_ m8 vmm . .aron mvm «NH 2w a 29 Me H NMe2 Fe ER '72 Me H 4,, NMe2 | . E,.NlCI2 NiCI2 @ azo (5)—(Bj-Ligands ‘ ©R (§)-(B)—Ni Catalysts E=S; RzMe,Et,n-Pr,l-Pr, n-Bu,t-Bu,i—Pent,Bz)Ph, 4—Tolyl (SB—65) E—Se; RzMe,4—ClPh (70,723 Me H ’III NMe2 I . Fe E/N‘C'2 NiCl2 ~—Ep Et2O (5)-(Bj—Ligands 4¥_ R ' ER (5)-(Bj—Nl Catalysts E25; R:Me,i—Pr,t—BU, 4-Tolyl (BE—69) E:Se; RzMe (71) Sf the appropriate signals. The enantiomeric shift Clifference AAS was also affected by the temperature as shown in figure 17 . 76 .mcmucmmlalaxconmlv mo Esuuommm mzz cououm "ma wusmflm ehMM 6%JQ QlJ. AqlN ,Qrfiv ,Qlfl. £§.m 8.n. 0.8. {rFPrPrPPPP-PPBPPPpPPPPP—[plrbprFPbp—VPPPPPPPPkfihpPPFLFP—rbppPrPPPP—rPPFPpbh—rhrrpr_ 77 .mHUQU ca .mAEopvsm .ucmwmwm unflnm Hmuaro z e~.o sea oumuspanascmrclMlasauoelAme 6:4 lime z m.o mo mzz cououm Any .wumu>usnaaconalmlaanumz no Esuuomam mzz cououm Am. “0H mesmem .9.8 e N e.rE e.w Q.m P>P>_>DDFPFDD> F>>b>>bb>>bhPb»Pbbi—thbbbbhbbbbhhthD>—: 8. m S .J n. a ®§OOQ\/ACQ ens—8%.: 4% j 03‘ .l 78 k“ 21°C ”*==.. 35°C 50°C UMM 4. U ML iFigure 17: The Magnitudes of AA8 of (R) And (S)-Methyl-3- phenylbutyrate (0.5 M) with Chiral Shift Reagent, Eu(dcm)3, (0.27 M) in CDCl3 at Different Temperatures. 79 Me Chiral H Me /L\ catalyst 3 DH Cl + CIMQW > DHM C13) EtZO H Me H Me .9 KM004)N3'O4_ ’)i\/COOMe (14) pm \. ' Ph MeOH,TSOH The Grignard cross-coupling reaction shown in eq.l3 was studied by using different nickel, palladium, and platinum complexes of ferrocenylamine sulfides and selenides. The optical yields were catalyst dependent and there was no significant difference in the chemical yields that remain more than 92% in all reactions. The absolute configuration of the coupling product 75 is determined by the configuration of the catalyst used since all ferrocenylamine complexes used in this work have (S,R) configuration and gave the coupling product R-75, while the (R,S)-catalysts used before94 gave S-75. Platinum catalysts gave consistently higher optical yields than their palladium analogs shown in table 9 or have loeen reported.94 Entries 6,7 showed that changing from sulfide to selenide or having two sulfide groups as in eentries 4,5 for palladium and platinum catalysts did not ‘affect the optical yield significantly. 80 Table 9: Asymmetric Grignard Cross-Coupling Reactions by Using Palladium and Platinum Complexes of Chiral ligands of the Type (S,R)(HS-C5H3—l-CH(Me)NMe2- 2-ER1)Fe(n5-C5H4-R2). Entry E R1 R2 M Chemical Optical Configuration Yield(%) Yield(%) 1 S Me H Pd 94 26 R 2 S Me H Pt 95 35 R 3 S i-Pr H Pt 93 31 R 4 S Me SMe Pd 92 27 R 5 S Me SMe Pt 93 37 R 6 Se Me H Pd 94 28 R 81 The effect of the alkyl or aryl sulfide substituents on the optical yield by using nickel complexes of ferrocenylmonosulfides is shown in table 10. Methyl sulfide (entry 1) gave considerably higher optical yield than those with straight or slightly branched alkyl sulfides (i.e. Et, n-Pr, i-Pr, n-Bu, and i-Pent) in agreement with those reported for palladium complexes.94 It was also reported that changing the dimethylamino group in PPFA/NiC12 to diethylamino reduced the optical yield of the coupling product of eq.4 from 63% to 35% ee.55 Nickel catalyst 61 with t-Bu monosulfide substituent gave the highest ee (36%) among the series due to the steric factor. Aryl groups gave the lowest optical yield and that could be due to their planarity. Increasing the optical yield by the steric factor for nickel catalysts induced us to examine the catalytic activity of the nickel complexes of ferrocenylamine disulfides (table 11). The optical yields were in general higher than those obtained from monosulfides (table 10) and the highest was again with t-Bu disulfide substituent (45% ee). Nickel complexes of ferrocenylamine selenides did not give significantly higher optical yields than their sulfideanalogs as shown in table 12. In summary the data obtained with ferrocenylamine sulfide or selenide catalysts contain several significant features: (a) Nickel and platinum catalysts gave significantly higher enantiomeric excess than their palladium analogs. 82 Table 10: Asymmetric Grignard Cross-Coupling Reactions with Chiral Ferrocenylsulfide Nickel Catalysts (56-65). Entry Catalyst Chemical Yield Optical Yield Configuration <%) (%) 1 56 97 30 R 2 57 96 14 R 3 58 94 14 R 4 59 95 26 R 5 6O 94 15 R 6 61 94 36 R 7 62 94 15 R 8 63 96 12 R 9 64 95 10 R 10 65 93 12 , R 83 Table 11: Asymmetric Grignard Cross-Coupling Reactions with Nickel Complexes of Chiral Ligands of Type (S,R)(n5—c5H3—l-CH(Me)NMe2—2—SR)Fe(n5—c5H4—SR). Entry R Chemical Yield Optical Yield Configuration (%) (%) 1 Me 95 37 R 2 i-Pr 94 29 R 3 t-Bu 92 45 R 4 p-Tolyl 93 29 R 84 Table 12: Asymmetric Grignard Cross-Coupling Reactions with Nickel Complexes of Chiral Ferrocenylamine Selenides of Type (S,R)(NS-C5H4-R1)Pe(n5-C5H3— l-CH(Me)NMe2-2-SeR2) (70-72). Entry R1 R2 Chemical Yield Optical Yield Configuration (%) (%) 1 H Me 96 31 R 2 SeMe Me 94 41 R 3 H ClC6H4 93 29 R 85 (b) Ferrocenylamine disulfides give in general higher optical yields than those with monosulfide group. (c) Catalysts with t-butylsulfide group gave higher optical yield than those with alkyl or aryl group for both ferrocenylamine mono-and disulfide series. (d) There is no significant difference in the enantiomeric excess when sulfide or selenide groups were introduced to the catalysts. (e) All (S,R)-ferrocenylamine sulfides and selenides complexed to Ni, Pd, and Pt gave the coupling product 75 with R configuration while (R,S)-ligand gave the S enantiomer. In general, the in situ nickel catalysts give the same trend with higher stereoselectivity than their palladium analogs reported in this work or previously.94 Therefore, it can be assumed that they are structurally and mechanistically similar. It should be noted that this assumption was also made by Kumada for the ferrocenyl- phosphine nickel complexes prepared in situ.35 The plausible mechanism is shown in scheme 12. The key step in this mechanism should be the coordination of the alkyl chloride with the metal M, which should be selective, to give the diastereomeric transition state or intermediate 77. The optical purity of the coupling product is determined at this stage since both transmetalation and reductive elimination steps are considered to occur with retention of 86 configuration at the chiral carbon.35 The role of the amino group is manifested in the transmetalation step that involves breaking of the N-M bond and forming an N-Mg bond (intermediate 78). 87 &Me .NMez EaNl-Cl 8 T] 0 D Me I PhCHCI WE) Cl2 H &Me NMe2 EaNi-CI .9 H \Me Pn:>\\V//::\ (R)-Product CIMgCH2CH1CH2 T1 m U.- :\ I\ 77 Me phCRCl H§Ne 2 @JKIWLE s—Ni-CHZCHfCH2 Fe 8 t—wm AW 79 78 MgCI2 E=S,Se Scheme 12: Proposed Mechanism for Grignard Cross-Coupling Reactions by Using Ferrocenylamine Sulfides Complexed to Nickel, Palldium, And Platinum. 88 C. Selective Hydrogenation. Selective hydrogenation of a particular double bond in highly functionalized molecule is always desirable and poses a continuing challenge in organic synthesis. Many transition metal hydrides have been applied in selective hydrogenation, including those of iron,114 copper,75'76'115 rhodium,116 118,122a 119 iridium,120 122 cobalt,117 ruthenium, osmium, 79b 121 chromium, palladium, and zirconium; in addition to the nontransition metal hydrides mentioned in the introduction. Homogeneous hydrogenation by transition metal complexes has also played a key role in the fundamental understanding of catalytic reactions. Important recent developments have 81,123 focused on kinetic and mechanistic aspects as well as theoretical124 investigations of this important class of reaction. However, many of these systems were not useful in synthetic scale for a number of reasons.117 They are as follows: (a) Lack of selectivity toward either isolated double bond or susceptible functionality. (b) The catalyst is inhibited by excess substrate.67a (c) The lifetime of the catalyst is short and the rate of reactions relatively slow, thus leading to poor yields and turnover numbers. (d) The catalyst is not air stable and once obtained should be used. Palladium ferrocenylamine sulfide catalysts by far overcome these problems. These catalysts, as will be shown later, are very selective toward isolated double bonds and compatible 89 with many function groups. In addition, they are air stable, can be used in less than 0.3% relative to the substrates and their reactions are relatively fast and give quantitative yields in many cases; therefore, they are good candidates for synthetic applications. Acetone was used as a solvent with palladium catalysts unless solvent effect was under investigation. Meanwhile acetone-water in 9:1 ratio was used with platinum complexes to give heterogeneous condition, since in acetone no hydrogenation was observed. The hydrogen pressure was 104 Psi for all cyclooctadiene and cyclohexadiene hydrogenation and 80 Psi for other substrates. 1. Selective Hydrogenation of 1,3-Cyclooctadiene to Cyclooctene. Selective hydrogenation of cyclooctadiene has been a subject of a number of papersll7'125'127 128 It and patents. is catalyzed, in the present work, by palladium or platinum ferrocenylamine sulfide or selenide complexes(46-50, 53, 55, 80). In some cases, induction time was observed before the hydrogen uptake starts. Figure 18 shows how hydrogen pressure is changed by time with different catalysts. It should be mentioned here that the compounds present after each reaction were 1,3-cyclooctadiene, cyclooctene, and cyclooctane. The ratios of (cyclooctadiene + cyclooctene): cyclooctane were determined by using GC, while the 1,3- cyclooctadiene: cyclooctene ratios were calculated by 90 Pressure (Psi) 1 10 105 '74.: + Get. 46 IL . -+- Get. 47 100 1': v + Canals 96 n ‘5' Get. 49 * Get. 50 II + —l 907 1'. “V 5 85‘ ‘a 80— " 75" 70 I I I I I I I T I | I I 0 2 4 8 8 1O 12 14 18 18 2O 22 24 Time (h) Figure 18: Hydrogen Pressure Drop Profile for The Hydrogenation of Cyclooctadiene Catalyzed by 46—50. 91 integration of the 1H NMR spectrum of the product after distillation in the olefinic region. As shown in figure 19 the outer olefinic protons of the diene and the olefinic protons of the monoene appear around 5.6 ppm, while the central protons of the diene show up at 5.8 ppm; thus the monoene to diene ratios were given by: Monoene = A5.6 - A5.8 Diene A5.8 where A is the 1H NMR area under peaks at the specified ppm. The results presented in table 13 showed that both selectivity (% cyclooctene/(% cyclooctene + cyclooctane) and conversion (% cyclooctene + % cyclooctane) can reach up to 100%. Palladium catalyst 47 (R = Et) gave the best results where selectivity and conversion were 100% and 92% respectively. Palladium catalyst 50 (R = Bz) gave also high selectivity and conversion (100% and 93% respectively). The selectivity dropped when platinum catalyst 53 was used; that as explained129 because Pt-S bonds could be stronger than Pd-S bonds, which their breakage is important to the hydrogenation of 1,3-cyclooctadiene. Hydrogenation of 1,3- cyclooctadiene failed completely when palladium or platinum ferrocenylamine selenide catalysts 55 and 80 were used under the same conditions, possibly because Pd-Se and Pt-Se bonds are stronger than Pd-S bonds. 92 all Reaction Products ss- su :7 ”f5 . s“ Figure 19: 1H NMR Spectrum of 1,3-Cyclooctadiene (top), The Reaction Products upon Its Hydrogenation (middle), And Cyclooctene (bottom). Table 13: Selective Hydrogenation of 1,3-Cyclooctadiene by Using Palladium And Platinum Catalysts. Entry Catalyst Reaction 1 46 2 47 3 48 4 49 5 50 6 53 7 80d 8 55 a without the induction time which was observed only for catalysts 47, ,fi\ Timea L¥_/] % 16 13.06 10 8.15 3 14.9 5 3.81 3.5 0.0 13 7.76 No hydrogen No hydrogen 50 and 53 (4.5, 93 Conversionb Selectivity 80. 91. 76 69. 82. 57. uptake uptake b %cyclooctene + %cyclooctane c %cyclooctene / 05 85 .73 67 72 18 l, 6 0. 8. 26. 12 35. and 1.9 h respectively) % .03 31 52 .28 O6 86. 91. 85. 96. 100. 92 08 85 O4 19 00 .24 (%cyclooctene + %cyclooctane) d (n5H5)Fe(USH3’1-CH(Me)NMeZ-2-SeMe)PdC1288 92. 100. 90. 72. 82. 60. 99 00 23 43 72 91 C 94 2. Selective Hydrogenation of 1,3-Cyclohexadiene to Cyclohexene. The palladium catalysts 41—45 were also examined for the selective hydrogenation of cyclohexadiene to cyclohexene and the results were listed in table 14. The induction time and the hydrogen uptake vs time were recorded and presented in figure 20. After the hydrogen uptake stops, the products were distilled from catalyst and analyzed by GC. Comparison of tables 13 and 14 indicates that both selectivity and conversion were substrate dependent and although they were reduced in the hydrogenation of cyclohexadiene, they are still up to 76% (with catalyst 43, R = n-Pr) and 81% (with catalyst 41, R = Me) respectively. 3. Selective Hydrogenation of 2,3-Dimethyl-1,3-butadiene. Upon using palladium ferrocenylamine sulfides selectively in the hydrogenation of cyclic conjugated dienes, we decided to investigate their application in the hydrogenation of acyclic conjugated double bonds. Table 15 shows the results of the hydrogenation of 2,3-dimethyl-1,3-butadiene by use of catalysts 81-85. Preparation and characterization of these catalysts have been reported previously;95I130I131 however, their catalytic activities remained unknown. These catalysts were selected in order to investigate the effect of second sulfide substituent on both conversions and selectivities. The conversion in all cases were more than 99.5% and 95 Table 14: Selective Hydrogenation of 1,3-Cyclohexadiene by Using Palladium Catalysts. Entry Catalyst Reaction Conversion Selectivity _-_ coo % % % 1 46 19 18.79 60.98 20.23 81.21 75.09 2 47 20 19.36 62.47 18.17 80.64 77.47 3 48 19 22.47 58.99 18.54 77.53 76.0 4 49 19 22.56 54.92 22.52 77.44 70.92 5 50 8 22.09 56.09 21.82 77.91 71.99 a without the induction time which was 1.5 h for only catalysts 46 and 50 96 Pressure (Psi) 1 10 105 5.1.»; "— °"' ‘5 ’3. + c... 47 100 " + Get. 48 4 ‘5‘ Get. 40 95 * Get. 60 90 7 85 a 80 — \N‘x . 75 _ 70 I r7 I I T i l r l 0 1 2 3 4 6 6 7 9 10 Time In) Figure 20: Hydrogen Pressure Drop Profile for The Hydrogenation of Cyclohexadiene Catalyzed by 46-50. 97 .6223 .2: met: pea 6.8.33 .06 nb—xmufio .3208 con... .NI .o 2385 BE... .3 one . 5.693.02.23.29.28:222:2 9: 8.8 ....e of 9.: to as? ....e «16024180322479 8149862.322-39.82z«zo_ «.8 98 «am «.8 t8 me n«...« . «1383832299 889 30.592.22-39 I: 98 «.8 tea «.5 to 5.3... «.o 82202198188...er 889.«62522479 «.8 98 F.«« «.6 me. «.o 9.8 _ .«ozz«ro_mzmo£mzmo . 829308.329 n8. 8. a.» 0.5. 99 o 88?. , 822299608850 >:>=oe_om 5.22600 39 39 3o. 39 E pd 3:525 23 Ev 2:: H H U I H U m m m .0352 32:. 3.63:. .3330 2262a méamcodEo. Eco. 8 9562599 7.5668 co cozmcmoocgc m>=oo_mm ”me mime 98 a fairly good selectivities, up to 74.8%, were achieved. The hydrogen pressure drop profile is shown in figure 21. Initial turnover rates were high and reached 575 mol(mol Pd)‘l (h)‘l. The major product in all cases is 2,3-dimethyl—2-butene and this shows that both hydrogenation and isomerization have been,occurred in the process. Such phenomenon was also observed when different areneCr(CO)3 complexes were used as selective catalysts under initial hydrogen pressure 30 atm (ca 420 Psi) and 1600C.79b A Comparison of the required conditions for both classes of catalysts, for the hydrogenation of 2,3-dimethyl-l,3-butadiene, clearly shows superiority of palladium ferrocenylamine sulfide catalysts. The results presented in table 15 revealed that catalysts with p-tolylthio substituents (i.e. 82-85) are more selective (> 61%) than catalyst 81 with methylthio substituent (47%); however, the turnover rate was higher (575.7) with the latter catalyst. Morever, catalysts 84 and 85 with two p-tolylthio group were more selective (66.2% and 74.8% respectively) than their mono p-tolylthio substitunet analogs 82 and 83 (61.2% and 70.1%) respectively. The best catalyst was 85 in terms of obtaining high yield of the major product (75%) and high turnover rate (497). The (2,3-dimethylbutane + 2,3-dimethyl-l-butene): 2,3- dimethyl-Z-butene: 2,3-dimethyl-l,3—butadiene ratios were determined by GC. The 2,3-dimethylbutane: 2,3-dimethyl-l- 99 5 Pressure (Pei) .. + Cat. 81 8° + Get. 82 + . 75 J Oct 83 ‘9' Get. 84 70 1 * Cat. 86 85 J , .‘5‘5 80 1 - = 55 1 50 I I I I I I I O 0.5 1 1.5 2 2.5 8 3.6 4 Time In) Figure 21: Hydrogen Pressure Drop Profile for The Hydrogenation of 2,3-Dimethyl-1,3-butadiene Catalyzed by 81-85. ’9: 100 butene ratios were obtained by integration of appropriate peaks in the 1H NMR. The starting material, 2,3-dimethyl- 1,3-butadiene, shows a singlet at 1.9 ppm for 6 methyl protons and a doublet at 5 ppm for 4 olefinic protons while 2,3-dimethyl-2-butene shows only one singlet at 1.6 ppm in the proton NMR spectra. On the other hand, 1H NMR spectra of 2,3-dimethyl-1-butene has a peak at 4.6 ppm for two olefinic protons which is distinguishable from the doublet of the starting material. There is also a doublet around 0.9 ppm for 6 protons of terminal methyls. 1H NMR spectra of 2,3- dimethylbutane also shows a doublet around 0.9 ppm for 12 methyl protons and a multiplet for the other 2 protons around 1.4 ppm. From these data it may be concluded that the ratios of 2,3-dimethylbutane: 2,3-dimethyl-l-butene can be obtained by: 2,3-dimethylbutane = (A009 - 3A4.5)/6 2,3-dimethyl-1-butene A4.5 4. Selective Hydrogenation of 3-Methyl-1,3-pentadiene. Up to here, all substrates that have been hydrogenated have two equivalent double bonds (i.e. cyclooctadiene, cyclohexadiene, and 2,3-dimethyl—l,3-butadiene) and thus only one initial monoene product was obtained after each hydrogenation except for 2,3-dimethyl-l,3—butadiene where rearrangement of the double bond could be detected. Therefore we found it useful to investigate the selectivity 101 toward two environmentally different double bonds; 3-methyl- 1,3-pentadiene was a good example. The data obtained upon its hydrogenation with different palladium ferrocenylamine sulfide catalysts in acetone under 80 Psi initial hydrogen pressure are given in table 16. The reaction products after hydrogenation and distillation could be analyzed by using GC with 25 M ethyl silicon capillary column. It is not surprising that the terminal double bond was hydrogenated much faster than the more substituted one, because of a steric reason, to give 3-methyl—2-pentene as the major product. The selectivities and the conversions were as high as 94.8% and 100% respectively. A direct comparison between catalyst 82 with one p-tolylthio substituent and catalyst 84 with two p-tolylthio groups indicates again that the introduction of the second sulfide group increases the selectivity (from 80.7% to 90.5%), while the conversion decreased from 100% to 90%. 5. Selective Hydrogenation of 6,6-Dimethylfulvene. Palladium ferrocenylamine sulfide catalysts can also be used in the hydrogenation of more than one conjugated double bond in substrate as 6,6-dimethylfulvene as shown in eq.lS without increasing the amount of catalyst (< 0.3%). The selectivity was 91% as analyzed by GC. No reduction of the tetrasubstituted double bond was detected. It should be mentioned here that all tetrasubstituted and most trisubstituted conjugated double bonds were not reduced 7; $228 .9: not: new 68:33 .9: mbtfimfim 6:2QO 8 mé .«I .o Sammoa .35 Ba om.m 102 0.; «.«m «.o ...«m 82. «.«F Ame362.23.073-23:22:10. armoolvxmozaazéva $9_«_ona:_«_2i-m=«ozz«:o_ was 98 so «.5 «.« 3: «158.182.22-38. 6§«_oua_:_«_2i-w. «. 3 «.2 «.o a: «.« t .« nozzmzxoifmooumxmo A«e_..«_oua_:_«_2i-m_ «.8 oo . «.3 «.8 m... , o maszfamxmomumzmo :«z«.o§=§£ «.2 «.3 «.2 «.3 «.« «.o .«ozzfoazmofnxmo 3.; 3.; 3.; 3.; 3.; 3.; 33:06.3 coficméoo /L/\ /\_/\ It /\_/\ azflmo \ méafiano. Eoo. .m mcofigfié. TEEmEfiéN .o cozmcmmofi? 02.8.8 “or 298. 103 under these conditions. This limitation can be useful in gaining selectivity in polyene molecules. 63182 ‘15) H2 (80 psi) acetone RT. 8.9% 91.1% 6. Selective Hydrogenation of Styrenes. After successful selective hydrogenation of conjugated dienes and polyenes with palladium ferrocenylamine sulfide catalysts, it is of interest to probe further and investigate the reduction of double bonds conjugated to aryl groups. Hydrogenation of styrene has been achieved previously by use of many different transition-metal based catalysts such as a zirconium(III) complex [(Cp)22rH(CH2PPh2)]n where n = 100—300,122 [(PBt3)Ptc1(u- SEt)]2/SnC12,132 tetranuclear osmium complexes,133 Pd2(Az)2C12 where AzH = Azobenzene,134 [Ru(COD)(PMe2Ph)3] where COD = cyclooctadiene,135 Pt(PPh3)(p—CH3PhNH2)C12,136 and Cp2Ti(CO)2.137 Results of hydrogenation of styrene and its derivatives by different palladium ferrocenylamine sulfide catalysts are listed in table 17. The pressure drop profile is depicted in figure 22. Entries 1—4 indicates that styrene can be 104 Tablei7 Selective Hydrogenation 0f Styrenes by Using Ferrocenylamine Palladium Catalysts.a Entry Starting Material Catalyst TimeCh) Product Yield(%) / 1 81 0.67 >99 2 .. 82 0.25 .. >99 3 u 84 0.25 n >99 4 ~ 85 2.0 .. >99 // 5 81 1.0 >99 6 ~ 82 0.25 ~ >99 7 ~ 84 0.67 ~ >99 8 ~ 85 0.5 ~ >99 9 Eféi 82 0 5 91 5 10 H 85 48 H 69.9 / 11 82 18 41 105 Table 17(cont'd.). Entry Starting Material Catalyst Timefihj Product Yield(%) OMe OMe / 12 [53’ 82 23 31 Br / 13 82 48 no reaction / 14 82 48 no reaction 15 [i] 82 48 no reaction a Room temperature, 80 psi initial H2 pressure, 4.5 mL acetone, 3.725x10“3 mOI substrate, and 1xio'5 moi catalyst. 106 Pressure (Psi) 85 l j y l r I I o 5 io 15 20 25 30 36 40 Time (min) Figure 22: Hydrogen Pressure Drop Profile for The Hydrogenation of (1) Styrene, (2) p-Methylstyrene, (3) a-Methylstyrene, and (4) B-Methylstyrene Catalyzed by 82. 107 hydrogenated qualitatively in a short time (15 min) to ethylbenzene. In order to evaluate the activities of these catalysts, they are compared with others and results are summarized in table 18; the rates have been normalized by dividing the number of moles of substrate (styrene) by the number of moles of catalyst and pressure to give valid comparison. Catalysts used in this work (entries 1 and 2, table 18) have much higher turnover rates than other catalysts. Platinum catalyst of entry 5 in the presence of SnClZ is comparable to our catalysts; however, it requires higher temperature (600C) and initial hydrogen pressure (600 Psi) for an efficient hydrogenation reaction. Entries 5-8 (table 17) show the results of the hydrogenation reaction of 4-methylstyrene. Again, quantitative yields and short reaction times are two characteristics of these reactions. The 1H NMR spectrum of styrene and 4-methylstyrene upon hydrogenation are given in figures 23 and 24 respectively, which show the complete reduction of the double bonds in these substrates. The effect of pressure on the hydrogenation of 4-methylstyrene by use of catalyst 84 was investigated and it was found that even at 20 Psi initial H2 pressure the reaction can be conveniently performed. In acetone and at room temperature, the reaction times for quantitative hydrogenation of 4— methylstyrene to 4-ethyltoluene at 60, 40, and 20 Psi were 45, 65, and 90 min respectively. The solvent effect was also 108 _«_oem=s«_sim=«esz«:o_mzmoen_mxmo n __oen_=e_2m=«ezz«:oimzmo£m_._mo m «2 «ed 8-8 .28va0 e e? 8.4 8 «oazzifoaxeenavi m «2 88.0 8 «58361838.: 1. ««F 5.0 om cz«:n_n_«:ofcw«ao: m x53 we: a. Z «« 98 « v.53 we: we «« a; 2 8888 {we we as 8.2.98 «Em 7:8 a .2569 c. mam 8588.36 2 0536 .6 528393: «.2823 ”mp £an 109 .« .AmcmNGmQH>£umv coaumdmmouoxm com: mcmumum mo Enuuommm mzz ma "mm musmam tau m.L o.~ rim o.m m.m o... m.v 0.0 m.m o.w m6 OK 0.5 od m5 od . — . u n . v c _. . .... . l ”I . _ m n h a .. . ( l .n. ..._, u . . .. _ . . . _ m ._ _ _ _ _ ._ l. _ . . ... m _ . . . _ ... _ .n: . n .. .... V . _ u . . . _ if. ; . u _ -7 _. , _ m _ ._ .. . ... ... m . I... .... .. ... _ 1 . _ .. . .. .u __ ._ .__ ._ n __ o _ = 110 .AmcmsaouH>QQMIvv coaumcmmouo>m coma wcmumumamuoziv mo Esnuommm mzz EH new musmflm 1...... o N v my a L ..b-b--»l.lpl- p _.L.-Pi-ib.pL-tl.l.Ple » » —bl> pb » p . pb - p p p r» p p . b -fils - in ca Nu p p p p . - .lPL .PLiLIpIPLlrrLiplLl—lblbl 111 investigated at room temperature and 80 Psi initial H2 pressure by using catalyst 84; 4-methylstyrene can be hydrogenated completely (yield >99%) by use of acetone, chloroform, THF, and DMSO as solvents. The reaction times in these four solvents are 20, 40, 75, and 720 min respectively. These results show that acetone is the best among the four solvents investigated for the hydrogenation of 4-methylstyrene and that is in complete agreement with the previous results for selective hydrogenation of cyclooctadiene.131 Entries 9 and 10 table 17 represent the results of hydrogenation of a-methylstyrene by use of catalysts 82 and 85. As shown, the former catalyst is much more effective than the latter for the hydrogenation of this substrate. The hydrogenations of a few B—substituted styrene derivatives were examined by use of catalyst 82 and it was found that the B-methoxystyrene and B-methylstyrene are the only substrates that can partially be hydrogenated under the reaction conditions. The hydrogenation of more bulky substrates such as B-bromostyrene (entry 12, table 17), 8- nitrostyrene (entry 13), and 8,8-dimethylstyrene (entry 14) were failed. 112 7. Regio- and Chemoselective Hydrogenation of Carbon-Carbon Double Bonds Conjugated to Different Functional Groups. The logical extension of the hydrogenation of conjugated double bonds and styrenes is the reduction of carbon-carbon double bonds conjugated to different unsaturated functional groups which is an important transformation in organic synthesis and has gained recently considerable interest.138 Stoicheiometric amounts of LiAlH4,75 DIBAH,76 and Mg/MeOH.78 Herein we report the selective reduction of carbon-carbon double bonds conjugated to carbonyl, carboxylic acid, ester, amide, nitrile, and lactone. No reduction of any of the functional groups was observed. The reduction was performed by using molecular hydrogen and catalyzed by the palladium ferrocenylamine sulfide catalysts 48, 82, 84, and 85. Table 19 (entries 1—12) shows that selective hydrogenation of double bonds could be achieved quantitatively in 0.25- 12 h. Representative 1H NMR spectra of the hydrogenated products of some of these substrates are shown in appendix, which indicate the complete hydrogenation of the carbon- carbon double bonds without affecting any of the functional groups. Selective reduction of some of these substrates were reported previously. Methyl vinyl ketone was reduced by use of HCo(CO)4139 or under hydrogen by using K3[Co(CN)5H]117 or C02(CO)8-di(tertiaryphosphine)69 as catalysts to give methyl ethyl ketone in 70%, 60%, and 91% respectively. K3[Co(CN)5H]117 was also used to catalyze the hydrogenation 113 Table 19: Conjugate Reduction with M0lecular H2/PdCIIj.a Entry Starting Material Catalyst TimeCh) Product Yield(%j o 0 1 2 0.5 100 I 2 3 0.5 100 O o 3 2 1 ()0 100 I H H 4 3 2 100 O o | 5 3 1.25 100 o o 7 I OMe 2 0.25 (JKOMQ 100 8 3 0.75 100 o o s fi)kNH2 3 0.25 (JKNHZ 100 CN CN I f 11 3 2.5 100 114 Table 19(cont'd.), Entry Starting Material Catalyst Time(n) Product 'Yieldc%) \ 12 (010 1 10 C10 100 0 0 13 6 1 8 <3 48 14 " 4 11 " 25 O O 15 b 4 5.5 6 100 O O 17 /4§/£OOH 1 48 ho reaction 18 /c«/<«/COOH 1 12 g”\/SS/COOH 100 COOH COOH 19 ==< 1 10 —«< 41 a Room temperature, 80 psi initial H2 pressure, 4.5 mL acetone, 3.725x10'3 m0l suDStrate, and 1x10'S m0! catalyst. 115 of 2—cyclopentenone and 2-cyclohexenone to cyclopentanone (10%) and cyclohexanone (75%) respectively; 2—cyclohexenone 140 and was also reduced by using Mo(CO)6/PhSiH3 C02(CO)6(PBu3)2/H2141 to give cyclohexanone in 25% and 86% respectively. Under our conditions methyl vinyl ketone, 2- cyclopentenone, and 2—cyclohexenone were hydrogenated in up to 100%, 48%, and 100% respectively (entries 1, 2, 13-15). Crotonic acid (entry 17) was not hydrogenated under this condition; however, extension of the conjugation, as in 2,4- hexadienoic acid (entry 18), allows the 100% reduction of the y-S double bond. Hydrogenation of methyl—2,4— hexadienoate was recently reported to give 1:1 mixture of a-B and 7-8 hydrogenated products by using Mg/MeOH.4b The order of reactivity (as presented in table 19 and figure 25) showed that double bonds conjugated to more basic carbonyl (i.e. amide or ester) are faster than those conjugated to more e.w.g. (i.e. carboxyl or nitrile). Another observation that flexible ketones (entries 1,2) which can adopt either transoid or cisoid are much faster than those locked in transoid conformation (entries 13—16). These observations indicate that both the double bond and the carbonyl group are simultaneously interacted with palladium. 116 5 Pressure (Psi) v ‘ 2 v \ 8 a 35 I T I 3 O 0.6 1 1.5 2 2.5 Time (h) Figure 25: Hydrogen Pressure Drop Profile for The Hydrogenation of (1) Methyl vinyl ketone, (2) Acrylaldehide, (3) Acrylic Acid, (4) Methyl acrylate, (5) Acrylamide, And (6) Acrylonitrile Catalyzed by 82. 117 8. Concluding Remarks. The results of this work reveals that palladium ferrocenylamine sulfide complexes are not only effective catalysts for cross-coupling reactions142 but also selective catalysts for hydrogenation of different dienes to 142,143 and carbon-carbon double bonds conjugated to monoenes different functional groups.144 These catalysts selectively hydrogenate mono- and disubstituted conjugated double bonds in the presence of tri- and tetrasubstituted olefins or isolated double bonds. Hydrogenation of different styrene derivatives shows also that they are susceptible toward steric hindrance. As a result, they can be useful in organic synthesis where, in a polyolefin, the hydrogenation of a less bulky conjugated double bond is desirable. This advantage plus their extreme air and moisture stability make them good alternative to other homogeneous organometallic hydrogenation catalysts used in synthetic scale. APPENDIX I-y 118 c; 3... r. A. .sz u mv av oesoQEou mo Esuuowmm mzz ma "om wuzoflm 21c .v :s. - . 3w 5* 0.? S _ .xrrtlrktlrkgiret___ _P_ %FLarrg;rrLIrHLlFrLL17+LIFEPLIri OZ 0.000N 0.00VN 0.000N 0.00Nm 0.000m "hm musmflm 0.000? OOO'OB 000'09 OOO'O? OOO'OB OOOO'O eauequtwaueqlx 00'00? OO'OBI 120 .Amz n me He unconsoo mo m2 ”mm wusmflm omm owm emu mmi oar m or: I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I — I I I I I . __ _ . _. _q_1 mom «rm mm” aw" m r a . 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I 4 4 __ 4. . 444... .44... ...4444.4.4..4. . .4 4 .4: .. 4. 4. ...._ .44 ....4 43.4-... o _ .4 .. ..... ..4_. .4. i ; . . .... .......... ...4... . . .. .4: 4. _. 3 4 4 _4 4 .4 a .:. -4 4. 4. 4.. ...... {4.4 4:44.... .4”. 44.. ...... :-. ... . : :%: .:.L;§ .:y..44_ 42 :4 4 4. 4 4 ..... 4 4 4 _ ._4.44p....a .. _ _ ...: . 4:1}. :. 4......4; 444.. 4 .4» 4 4.444.444... 4..- ..... _ . 1.4.... _ _ -4. 444 . .0!»'.I-7 .- 164 .Amcouomaouwam>nw4 coflumcwmouvxm com: wcouomHoume>lwlwcw|H mo Ezuuowmm mzz mH .mw wusmflm Inn. m.l 0.0 m. o.« r...“ o.w m.w o.m rim 0.? m.v MK 0.0 m6 :.__—.__4_.__4.__—fi—q_q—______—__4____4___J__:4_.:4___ __ _4 _ . [It I: on D O— P— ou Bu on a. 0.. IV .- In on n. .m as O. r. _ _ ._ p....4.._._..._4... 4 .__ 4 _ . 4 _ _ _ . _ 4.2.4.... REFERENCES 10- ll- 12- l3- 14- 15- 16- 165 REFERENCES Bosnich, B.; Fryzuk, M.D. Top.Stereochem. 1981, 12, 119. Hoyash, T.; Kumada, M. Acc. Chem. Res. 1982, 15, 395. Bosnich, B. 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Naiini, A.A.; Ali, H.M.; Brubaker, C.H., Jr. in preparation. Ali, H.M.; Naiini, A.A.; Brubaker, C.H., Jr. in preparation. :NICHIGRN STQTE UNIV. L gum m I! H 11115111 129300629