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12/13 = 0.923C-D,  µ= 12x2/(12 + 2) = 24/14 = 1.714Eqn. 3 Eqn. 4 Eqn. 2  3 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¡C1800 psiDDDDDDm-CBPADDDDDDODDDDDDO+DDDD+185 ¡C1800 psiDDDDDDm-CBPADDDDDDODDDHDDD334a4b5b5aDiradical Intermediate 8 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p-MeOHNOPMPOPhH+CH3CD3DDDDDPd(OAc)2(100 mol%)1,4-dioxane 90 ¡CONOPMPPhCD2ONOPMPPhDDDDD++6kHkD=3.55 9 !/D>%K%&W5!S,'(/,=!T)&/&M(!177(=/L!1B;&M(.'!6&'(FN((!O;(K.2&)(!E./.2FG(-!6F-;&2F),)$"!!"#$#I!J(=K.',)/,=!?'.2F),)L!Q&;3&)(!<(.=/,&'!!OK(!Q&;3&)(!;(.=/,&'d!aK,=K!-()=;,N()!/K(!7&;3./,&'!&7!)BZ.;)!7;&3!7&;3.2-(KF-(!K.)!N(('!M;&M&)(-!/&!(+M2.,'!/K(!&;,Z,')!&7!2,7(#!V,'=(!,/)!-,)=&H(;F!,'!"P@"!NF!?2(^).'-;!UB/2(;&Hd$$!(+/('),H(!;()(.;=K!K.)!N(('!-&'(!/&!B'-(;)/.'-!,/)!3(=K.',)3!.'-!,'!"R4Rd!U;()2&a$5!M;&M&)(-!.!3(=K.',)3!7&;!/K,)!M;&=())!/K./!,'H&2H(-!7&;3./,&'!&7!('(-,&2)!-B;,'Z!/K(!=&'H(;),&'!&7!W!/&!Q!.'-!&7!M!/&!L!C/D>%K%&QD#!HOHHHOHOOHHOHHOHOHHHOHOHHOOHHHOHHDOHOOHHOHHOHOHHHODODHOOHHOHHOHHOHOOHHHOHROHHOHHOHOOHHHOHROOOOHOHHOHHOHHOHHOHOHHOHHOHHOHHOHHOOHOHHOHHOHOOHHHOHROHOOOHOHHOHHOHOHHOHOHHOOOHROHH2OROH!-Glucose"-Glucose+""-[1,1'-H]trehalose,""-[1,1'-2H]trehalose,Nucleophilic Double DisplacementOxocarbenium Ion Intermediate Reaction 10 &/D>%K%&Q5!Q&;3&)(!<(.=/,&'L!U;()2&ag)!6FM&/K(),)!!U(''(;$0!)/B-,(-!/K()(!;(.=/,&')!,'!>$*!.'-!-,-!'&/!&N)(;H(!-(B/(;,B3!,'!/K(!M;&-B=/)d!=&'/;.-,=/,'Z!U;()2&ag)!KFM&/K(),)!/K./!,'H&2H(-!('&2,G./,&'#!U;()2&a!;(H,)(-!K,)!3(=K.',)3!.'-!M;&M&)(-!KF-;,-(!)K,7/!,')/(.-!&7!('&2,G./,&'#$4!O&!=&'7,;3!/K,)!KFM&/K(),)d!K(!B)(-!$8-(B/(;&Z2F=(;.2-(KF-(!CAAD!.'-!&N)(;H(-!/K(!7&;3./,&'!&7!"8-(B/(;&-,KF-;&+F.=(/&'(!CAJD!a,/K!I0h!&7!/K(!-(B/(;,B3!)/,22!;(/.,'(-!C/D>%K%&ND#!OK,)!;(.=/,&'!(+M2.,'(-!/K(!.N)('=(!&7!-(B/(;,B3!,'!M;&-B=/)!B'-(;!U(''(;g)!=&'-,/,&')#!!/D>%K%&N5!<(H,)(-!J(=K.',)3L!Q&;3&)(!<(.=/,&'!!T'!.--,/,&'!/&!/K(!3(=K.',)3)!3('/,&'(-!.N&H(d!ST1!.'-!-(B/(;,B3!/;.=(;!)/B-,()!K.H(!N(('!(3M2&F(-!,'!a,-(!.;;.F!&7!=&'-,/,&')!/&!.=K,(H(!3(=K.',)/,=!,'),ZK/!.'-!7B;/K(;!&M/,3,G./,&'!&7!/K(!;(.=/,&')#!!T'/;&-B=/,&'!&7!-(B/(;,B3!,'/&!3&2(=B2()!K.)!M;&H(-!/&!N(!.'!())('/,.2!/&&2!,'!B'-(;)/.'-,'Z!=K(3,=.2!.'-!N,&2&Z,=.2!/;.')7&;3./,&')!.'-!,'!/K(!7&22&a,'Z!)(=/,&'d!a(!a,22!-,)=B))!K&a!,/!.2/(;)!/K(!,'/(;.=/,&'!&7!-(B/(;,B382.N(2(-!3&2(=B2()!,'!.!N,&2&Z,=.2!('H,;&'3('/d!2(.-,'Z!/&!/K(,;!.MM2,=./,&'!.)!3(-,=,'.2!.Z('/)#!!!HOOHHHOOHOHHOHOHOHHOHOHHOHHHO2(7)(8)(7A)(8A)OOHHOHHOOHOOHOH(9)(10)SugarsRNAOHOOHHDOHCa2+pH 12-H2OOHOOHDCa2+OHOOCa2+HDOHOHOHDH2O- OH-- Ca2+1111(a)11(b)12 11 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"#5#5!S,'(/,=!T)&/&M(!177(=/L!V(H&72B;.'(!V(H&72B;.'(d!.!H&2./,2(!.'()/K(/,=!-;BZd!,)!=&33&'2F!B)(-!7&;!Z('(;.2!.'()/K(),.#!OK,)!-;BZd!3(/.N&2,G(-!NF!/K(!=F/&=K;&3(!A04X!$1"!('GF3(d!Z('(;./()!K(+.72B&;&,)&M;&M.'&2d!=.;N&'!-,&+,-(!CE*$D!.'-!72B&;,-(!.',&'!CQ8D#$R!O&!,'H()/,Z./(!/K(!(77(=/!&7!-(B/(;./,&'!&'!,/)!MK.;3.=&^,'(/,=!M;&7,2(d!.!2.N,2(!E86!),/(!a.)!-(B/(;./(-#!OK(!3(/.N&2,)3!)/B-F!M(;7&;3(-!&'!/K(!M;&/,./(-!.'-!-(B/(;./(-!)(H&72B;.'(!)K&a(-!.!ST1!&7!"Id!&M(','Z!.!M&)),N,2,/F!&7!B),'Z!-(B/(;,&)(H&72B;.'(!.)!.!M&/('/,.2!=.'-,-./(!a,/K!.!2&'Z(;!."Y$!C/D>%K%&AJD#5X!!&/D>%K%&AJ5!S,'(/,=!T)&/&M(!177(=/L!V(H&72B;.'(!!!"#5#0!S,'(/,=!T)&/&M(!177(=/L!A.;&+(/,'(!A.;&+(/,'(d!.'!.'/,8-(M;()).'/!-;BZ!,)!B)(-!/&!/;(./!3.y&;!-(M;()),H(!-,)&;-(;)!.)!a(22!.)!K&/!72.)K()!.'-!',ZK/!)a(./)#!>B(!/&!/K(!3(/.N&2,=!M;&7,2(!&7!M.;&+(/,'(!/K./!,'=2B-()!E\A$>@8,'-B=(-!3(/.N&2,)3!&7!/K(!3(/KF2('(-,&+F!;,'Z!/&!M;&-B=(!.!=.;N('(!)M(=,()!/K./!=.'!,;;(H(;),N2F!=&H.2('/2F!N,'-!/&!/K(!A04X!('GF3(!C/D>%K%&AMDd!,/!,)!'&/!;(=&33('-(-!/&!M./,('/)!/.^,'Z!.--,/,&'.2!-;BZ)#!T/!=.'!)2&a!-&a'!/K(!3(/.N&2,)3!C-(/&+,7,=./,&'D!&7!&/K(;!-;BZ)!.)!A04X!('GF3(!,)!;()M&'),N2(!7&;!/K(!3(/.N&2,)3!&7!.23&)/!4Xh!&7!3(-,=./,&')#!OF3CF3CFOF3CF3CFDDOF3CF3CFOHDOF3CF3CFOHHOHF3CF3C+CO2+F-kDkH=17 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Pd/C(en), H2THF/D2O (7:3), 50 oC12 hHHODD(93%)10% Pd/CD2O, 100 oC 1 hNNR'RCl-HHHNNR'RCl-DDD(90-96%)(99%) 30 !/D>%K%&MJ5!A-YE8E./.2FG(-!6Y>!1+=K.'Z(!,'![B=2(&),-()!!OK(!/(=K',xB(!3('/,&'(-!.N&H(!a.)!.2)&!B)(-!/&!,'/;&-B=(!-(B/(;,B3!,'/&!-(;,H./,H()!&7!MF;,-,'(d!,'-&2(d!.'-!MF;,3,-,'(#!OK(!(77(=/!&7!A-!,'!.=/,H./,'Z!.;&3./,=!KF-;&Z(')!M.H(-!/K(!a.F!7&;!,'=&;M&;./,'Z!-(B/(;,B3!,'/&!H.;,&B)!N,&.=/,H(!3&2(=B2()d!2,^(!)B27.3(/K.G,'(d!'.2,-,+,=!.=,-!.'-!.'/,MF;,'(!C16HC@%&LD#"IR!!16HC@%&L5!U,&.=/,H(!J&2(=B2()!!V.y,^,!*.-&8#"PX!=&3N,'(-!/K(!.N,2,/,()!&7!K(/(;&Z('(&B)!A-!/&!.=/,H./(!.;&3./,=!.'-!N('GF2,=!E86!N&'-)!.'-!.//(3M/(-!/&!,'/;&-B=(!-(B/(;,B3!./!N&/K!),/()!),3B2/.'(&B)2F!,'!N('GF2.-(','(#!mK('!/K(!;(.=/,&'!a.)!=.;;,(-!&B/!./!""X!eE!,'!/K(!M;()('=(!&7!"Xh!A-YEd!-(N('GF2./,&'!a.)!&N)(;H(-d!aK(;(.)!;(M2.=,'Z!/K(!=./.2F)/!a,/K!4h!A-YEC('D!./!"PX!eE!;(3.;^.N2F!M;&3&/(-!/K(!6Y>!(+=K.'Z(!;(.=/,&'!C/D>%K%&MMD#!!NNNNNH2OOHOHHHHHHOHHNNNNNH2OOHOHHHHHHODD10% Pd/C, H2D2O, 110 oC, 24 h95% D92% DH2NSHNOONNsulfamethazineNNOOOHnalidixic acidONNantipyrine 31 !!/D>%K%&MM5!A-YE8E./.2FG(-!6Y>!1+=K.'Z(!,'!U('GF2.-(','(!!A-YE86$8>$*8=./.2FG(-!3B2/,-(B/(;,B3!,'=&;M&;./,&'!,'/&!B'.=/,H./(-!2,'(.;!&;!N;.'=K(-!.2^F2!=K.,')!/K./!N(.;!.!=.;N&+F2d!KF-;&+F2d!(/K(;d!()/(;d!&;!.3,-(!3&,(/F!.'-!.;(!=&''(=/(-!a,/K!/K(!N('G('(!;,'Z!K.)!N(('!;(M&;/(-#"P"d"P$!?M.;/!7;&3!/K(!N('GF2,=!.=/,H./,&'!)K&a'!NF!K(/(;&Z('(&B)!A-d!K(./,'Z!/K(!;(.=/,&'!/&!.!/(3M(;./B;(!.)!K,ZK!.)!"@X!eE!-(3&')/;./(-!-(B/(;,B3!,'=&;M&;./,&'!./!&/K(;a,)(!'&'82.N,2(!=.;N&')!C/D>%K%&MLD#!!!/D>%K%&ML5!A-YE8E./.2FG(-!6Y>!1+=K.'Z(!,'!?2^F2!EK.,')!&7!?;&3./,=!E&3M&B'-)!!OK,)!(77(=/!K.)!.2)&!N(('!3,3,=^(-!NF!?/G;&-/!*.-&8#"P5!(3M2&F,'Z!A-YE!,'!/K(!M;()('=(!&7!)&-,B3!N&;&-(B/(;,-(!C[.U>0D!.)!.!;(-B=,'Z!.Z('/!/&!.=/,H./(!/K(!=./.2F)/#!OK(!;(.=/,&'!a.)!=&'-B=/(-!B),'Z!>$*!.)!.!M;,3.;F!)&B;=(!&7!-(B/(;,B3!.'-d!./!"5X!eEd!/K(F!.=K,(H(-!3&-(;./(!-(B/(;./,&')!./!B'.=/,H./(-!=.;N&')!C/D>%K%&MOD#!!NNNHNNHHHHHNNNHNNHDDDDD(94%)(94%)(97%)(17%)5% Pd/C(en)H2 (balloon) D2O, 180 oC, 24 hHHHHHHHHHHHH10% Pd/CH2 (balloon)D2O, 160 oC, 48hDDDDDDDDDDDDDD42%97%97%88%92%92%92% 32 !/D>%K%&MO5!A-8E./.2FG(-!6Y>!1+=K.'Z(!,'!?2^F2!EK.,')!!V.y,^,!*.-&8#!-(H(2&M(-!.'!(77(=/,H(!=./.2F/,=!,)&/&M(!(+=K.'Z(!;(.=/,&'!N(/a(('!6$!.'-!>$*!,'!/K(!M;()('=(!&7!A-YE!/&!Z('(;./(!>$#!OK(!>$!a.)!Z('(;./(-!,'!/K(!)F)/(3!B),'Z!"Xh!A-YE!,'!/K(!M;()('=(!&7!6$!./!;&&3!/(3M(;./B;(d!a,/K!>$*!)(;H,'Z!.)!/K(!-(B/(;,B3!)&B;=(#!OK(!>$!Z('(;./(-!a.)!(H('/B.22F!B)(-!7&;!A-YE8=./.2FG(-!&'(8M&/!=./.2F/,=!;(-B=/,&'!&7!7B'=/,&'.2,G(-!.;&3./,=!K.2,-()d!(M&+,-(d!',/;,2(!.'-!B')./B;./(-!KF-;&=.;N&')!a,/K!xB.'/,/./,H(!-(B/(;,B3!,'=&;M&;./,&'!(77,=,('=,()#"P"d"P0!V.y,^,!*.-&8#"P4!.2)&!-(3&')/;./(-!.!2,xB,-8MK.)(!;(-&+!)F)/(3!N(/a(('!$e!.2=&K&2)!.'-!^(/&'()d!,'!/K(!M;()('=(!&7!/K(!A-YE86$8>$*!)F)/(3d!/K./!M;&-B=(-!.!3,+/B;(!&7!-(B/(;,B382.N(2(-!$e!.2=&K&2)!.'-!^(/&'()#!OK(F!KFM&/K(),G(-!/K./!/K(!$e!.2=&K&2!a.)!&+,-,G(-!/&!/K(!=&;;()M&'-,'Z!^(/&'(!B'-(;!/K(!KF-;&Z('./,&'!=&'-,/,&')!.'-!/K(!KF-;&Z('./,&'!&7!/K(!.2,MK./,=!^(/&'(!/&!/K(!=&;;()M&'-,'Z!$e!.2=&K&2!a,/K!-(B/(;,B3!,)!;()M&'),N2(!7&;!/K(!-(B/(;,B3!,'=&;M&;./,&'!C/D>%K%&MRD#!!/D>%K%&MR5!A-YE8E./.2FG(-!6Y>!1+=K.'Z(!,'!?2=&K&2)!&OHHHHHHH10% Pd/C5 Mol% NaBD4 D2O, 130 oC, 18 hOHDDDDDD97%97%27%OHHHHHDDDDDOo-Ph (59% D)m/p-Ph (26% D)HHHHHOH10% Pd/C, H2D2O, 110 oC (reflux)18 hCD3DDDDDOHCD3DDDD+O(77%)(96%)(95%)(93%)12(1:2 = 60:40)(66%) 33 c/,2,G,'Z!/K(!=&'=(M/!&7!,0-%,.9!>$!Z('(;./,&'d!V.y,^,!*.-&8#"P@!-(H(2&M(-!.!1/5[83(-,./(-!6Y>!(+=K.'Z(!;(.=/,&'!&7!.2^F'()!/&!M;&-B=(!-(B/(;./(-!.2^F'()!,'!.!3,+/B;(!&7!>$*!.'-!O6Q!./!;&&3!/(3M(;./B;(#!OK(F!.2)&!-(H(2&M(-!.!3(/K&-!&7!A-YU[!CM.22.-,B3YN&;&'!',/;,-(D!=./.2FG(-!;(Z,&)(2(=/,H(!;(-B=/,&'!&7!.2^F'()!/&!Z,H(!-(B/(;./(-!.2^('()!a,/K!(+=(22('/!-(B/(;,B3!=&'/('/#!?!H.;,(/F!&7!;(-B=,N2(!7B'=/,&'.2,/,()d!)B=K!.)!',/;&!Z;&BM)d!N('GF2!(/K(;)d!OUV!(/K(;)d!.'-!),2.'()!a(;(!a(22!/&2(;./(-!B'-(;!/K()(!;(.=/,&'!=&'-,/,&')!C/D>%K%&MWD#!!/D>%K%&MW5!A-YU[8E./.2FG(-!>(B/(;&Z('./,&'!&7!?2^F'()!!*)K,3.!*.-&8#"I$!K.H(!.2)&!;(M&;/(-!.!A-8=./.2FG(-!-(=.;N&+F2./,H(!-(B/(;./,&'!M;&=())!B'-(;!KF-;&/K(;3.2!=&'-,/,&')#!OK(F!KFM&/K(),G(-!/K./!A-!B'-(;!KF-;&/K(;3.2!=&'-,/,&')!,'!>$*!2(.-)!/&!/K(!7&;3./,&'!&7!M.22.-,B3!-(B/(;,-(!/K./!)(;H()!.)!.!;(.Z('/!7&;!/K(!-(=.;N&+F2./,&'!&7!7;((!=.;N&+F2,=!.=,-)!.'-!-(=.;N&'F2./,&'!&7!.2-(KF-()d!.'-!=&'=B;;('/2F!-(B/(;./(!/K(!)BN)/;./()!C/D>%K%&MQD#!Me2PhSiMe2PhSiDMe2PhSiDDDMe2PhSiDMe2PhSiDDDD2, 0.3% Pd/BN (0.10 mol%)MS(molecular sieves) 4A 2,6-lutidine (1 eq.)pyridine, 25 oC, 2.5 hD2, 0.3% Pd/BN (0.6 mol%)pyridine, 25 oC, 9 hMS (molecular sieves) 4A 2,6-lutidine (1 eq.)pyridine, 25 oC, 2.5 hH2, 0.3% Pd/BN (0.10 mol%)Et3N D2O, THF (1:1)50 oC, 48 h(90%)(93%)(92%)(10%)(93%)(85%)(88%) 34 !/D>%K%&MQ5!A-8E./.2FG(-!>(=.;N&+F2./,H(!>(B/(;./,&'!!"#0#5#5!A/8E./.2FG(-!6Y>!1+=K.'Z(!E&3M.;(-!/&!A-YE86$8>$*d!A/!K.)!N(//(;!;(.=/,H,/F!/&a.;-)!.;&3./,=!KF-;&Z(')#!_.;'(//!*.-&8#"PId"PP!;(M&;/(-!.!A/8=./.2FG(-!CM;(8;(-B=(-!M2./,'B3!&+,-(!a,/K!>$D!6Y>!(+=K.'Z(!;(.=/,&'!B),'Z!>$*!7&;!/K(!-(B/(;./,&'!&7!N('G&,=!.=,-!.'-!,/)!)&-,B3!).2/d!N;&3&N('G('(d!,)&M;&MF2!N('G&./(d!.',2,'(d!',/;&N('G('(d!M8',/;&N('G&,=!.=,-d!MK('&2d!MF;,-,'(d!.'-!/;,3(),=!.=,-#!!V.y,^,!*.-&8#"PRd"RX!!.2)&!,'/;&-B=(-!.!-(B/(;./,&'!3(/K&-!7&;!.;&3./,=!;,'Z)d!B),'Z!/K(!A/YE8>$*86$!)F)/(3#!OK(!;(.=/,&'!a.)!&M(;./(-!,'!/K(!/(3M(;./B;(!;.'Z(!&7!$4q"PX!eE#!OK,)!3(/K&-!a.)!B)(-!/&!,'H()/,Z./(!-(B/(;./,&'!&7!.;&3./,=!;,'Z)!M&))()),'Z!.'!(2(=/;&'8-&'./,'Z!Z;&BM!2,^(!MK('&2d!aK,=K!)K&a(-!(+=(22('/!-(B/(;,B3!,'=&;M&;./,&'!./!/K(!.;&3./,=!;,'Z#!>(B/(;./,&'!&7!.;&3./,=!;,'Z)!M&))()),'Z!.'!(2(=/;&'8a,/K-;.a,'Z!Z;&BM!2,^(!,'!N('G&,=!.=,-!)K&a(-!2&a(;!;(.=/,H,/Fr!/K,)!a.)!=&3M(')./(-!NF!.'!,'=;(.)(!,'!/K(!/(3M(;./B;(#!T'/;&-B=/,&'!&7!.'!(2(=/;&'8a,/K-;.a,'Z!Z;&BMd!)B=K!.)!',/;&d!)/;&'Z2F!-,3,',)K(-!/K(!;(.=/,H,/F!&7!)BN)/;./()!(H('!./!K,ZK!/(3M(;./B;()#!V.y,^,!*.-&8#"R"!,'H()/,Z./(-!A/8=./.2FG(-!;(.=/,&')!,'!.!6$!7;((!('H,;&'3('/!(3M2&F,'Z!A/YE!,'!.!3,+/B;(!&7!,)&M;&MF2!.2=&K&2d!=F=2&K(+.'(!.'-!>$*!,'!aK,=K!G(;&!H.2('/!A/!3(/.2!a.)!)(278.=/,H./(-!NF!/K(!,0-%,.9!Z('(;./(-!6$!-(;,H(-!7;&3!,)&M;&MF2!.2=&K&2#!OK(!M;()('=(!&7!.=(/&'(!,'!/K(!;(.=/,&'!;()B2/(-!,'!/K,)!3(=K.',)/,=!,'/(;M;(/./,&'#!!COOHHOHHHH10% Pd/C, D2O250 oC, 4-5 MPa12 hCD3DODDDDDD(97%)(97%)o-Ph (98% D)m-Ph (98% D) 35 "#0#5#0!A-YA/!6FN;,-!E./.2FG(-!6Y>!1+=K.'Z(!OK(!),3B2/.'(&B)!B)(!&7!3B2/,M2(!=./.2F)/)!('.N2()!/K(!;(-B=/,&'!&7!;(.=/,&'!)/(M)!7&;!M(;-(B/(;./,&'!.'-!,)!=&)/!).H,'Z!,'!=&3M.;,)&'!/&!)/(Ma,)(!;(.=/,&')!a,/K!/K(!,'-,H,-B.2!B)(!&7!.!=./.2F)/#!J&;(&H(;d!=&3M&),/(!=./.2F)/)!K.H(!N(('!)K&a'!/&!M&))())!'&H(2!.'-!B',xB(!.=/,H,/,()!)B=K!.)!/K(!v,(Z2(;q[.//.!=./.2F)/!=&3M&)(-!&7!/,/.',B3!CO,D!.'-!.2B3,'B3!C?2D!&;!/K(!A-YA/!)BMM&;/(-!-('-;,3(;!=./.2F)/!7&;!M&2F3(;,G./,&'#"R$!OK(!B)(!&7!3,+(-!A-YE!.'-!A/YE"R5q"R4!&;!/K(!'&H(2!N,3(/.22,=!A-YA/!&'!.!=.;N&'!=./.2F)/"R@!a(;(!7&B'-!/&!N(!3&;(!(77,=,('/!,'!/K(!6Y>!(+=K.'Z(!;(.=/,&'!/K.'!/K(!,'-(M('-('/!B)(!&7!A-YE!&;!A/YE!C/D>%K%&MND#!J&-B/2a.!*.-&8#"RI!(+M.'-(-!&'!/K,)!a&;^!.'-!.MM2,(-!/K(!)F'(;Z,)/,=!(77(=/!,'!-(H(2&M,'Z!-(B/(;./(-!3(-,=,'.2!.Z('/)#!OK(!/;.')7&;3./,&')!a(;(!=&'-B=/(-!B),'Z!A-YEd!A/YE!.'-!<KYE!,'!/K(!M;()('=(!&7!6$!.'-!>$*!./!"@X!eE!/&!-(B/(;./(!H.2M;&3,-(d!MK('F/&,'!.'-!/;,3(/K&M;,3#!!/D>%K%&MN5!A-YA/!6FN;,-!E./.2FG(-!6Y>!1+=K.'Z(!!HHHHHH5% Pd/C (20%)H2 (balloon)D2O, 180 oC, 24h98%97%97%17%98%98%OHHHHHHDDDDDDOHDDDDD98%98%72%28%38%98%42%DDDDDDOHDDDDD98%5% Pt/C (20%)H2 (balloon)D2O, 180 oC, 24h99%98%98%97%98%98%DDDDDDOHDDDDD99%H2 (balloon)D2O, 180 oC, 24h5% Pd/C (20%)5% Pt/C (20%) 36 OK(!)F'(;Z,)/,=!(77(=/)!&7!A-8A/YE!a(;(!7B;/K(;!,'H()/,Z./(-!NF!>(;-.B!*.-&8#"RP!,'!aK,=K!/K(F!.MM2,(-!3,=;&a.H(!=&'-,/,&')!/&![.U>08.=/,H./(-!3(/.2!=./.2F)/)#!?!H.;,(/F!&7!.;&3./,=!.'-!K(/(;&=F=2,=!=&3M&B'-)!a(;(!,'H()/,Z./(-!.'-!/K(F!-(3&')/;./(-!),Z',7,=.'/!-(B/(;,B3!,'=&;M&;./,&'!,'!/K(!M;()('=(!&7!A-8A/!3,+/B;()!C/D>%K%&LVD#!!/D>%K%&LV5!A-YA/8E./.2FG(-!>(B/(;./,&'!B'-(;!J,=;&a.H(!E&'-,/,&')!!"#0#5#4!<K&-,B3!E./.2FG(-!6Y>!1+=K.'Z(!!V,3M2(!.2^.'()d!aK,=K!.;(!,'.=/,H(!)BN)/;./()!NF!3&)/!-(7,',/,&')!)K&a(-!(77,=,('/!-(B/(;./,&'!B'-(;!<KYE8=./.2FG(-!=&'-,/,&')!./!"@X!eE!,'!.!6$!7,22(-!)(.2(-!/BN(!B),'Z!>$*!.)!.!)&2H('/!.'-!/K(!)&B;=(!&7!-(B/(;,B3#![&/!&'2F!2,'(.;!.2^.'()!NB/!.2)&!/K(!=F=2,=!.'-!N;.'=K(-!.2^.'()!B'-(;a('/!-(B/(;./,&'!/&!.77&;-!/K(!=&;;()M&'-,'Z!7B22F!-(B/(;./(-!M;&-B=/)!a,/K!K,ZK!-(B/(;,B3!(77,=,('=,()!C16HC@%&OD#"RR!!16HC@%&O5&<KYE8E./.2FG(-!6Y>!1+=K.'Z(!,'!V./B;./(-!6F-;&=.;N&')!!"#0#5#@!J,)=(22.'(&B)!>(B/(;./(-!<.'(F8',=^(2!-(3&')/;./(-!.;&3./,=!6Y>!(+=K.'Z(!./!IX!eE!,'!>$*#!VBN)/;./()!,'H()/,Z./(-!B),'Z!/K()(!;(.=/,&'!=&'-,/,&')!a(;(!)&-,B3!=,''.3./(!.'-!)&-,B3!N('G&./(#$XX!<.'(F8[,!K.)!.2)&!(77(=/(-!6Y>!(+=K.'Z(!,'!/K(!M;()('=(!&7!>$*!/&!Z,H(!SH2NSDDDDD(87%)(35%)(43%)(36%)(99%)NaBD4150 oC, 2 hmwCD2 94%CD3 88%; CD2 90%; CD 90% 37 -(B/(;./(-!.;&3./,=)d$X"!Z2B=&)(d$X$!Z2F=&),-()d$X5!"d@8.'KF-;&K(+&)()$X0!.'-!H.;,&B)!&/K(;!=.;N&KF-;./()#$X$d$X4d$X@!JB^B3&/&!*.-&8#$XI!;(M&;/(-!6Y>!(+=K.'Z(!,'!&M/,=.22F!.=/,H(!N('GF2,=!=&3M&B'-)!2,^(!CGD8$8MK('F2M;&M'&,=!.=,-d!CGD8$8KF-;&+F8$8MK('F2.=(/,=!.=,-!.'-!CGD8$8.3,'&8$8MK('F2.=(/,=!.=,-!a,/K&B/!.'F!;.=(3,G./,&'!B),'Z!E&N.2/8?2B3,'B3!?22&F#!OK(!;(.=/,&'d!=&'-B=/(-!,'!>$*!B),'Z!)&-,B3!=.;N&'./(!C[.$E*5Dd!Z.H(!IX8PRh!-(B/(;./,&'!a,/K!**!H.2B()!;.'Z,'Z!7;&3!0@8RRh#!?!)&2,-8MK.)(!T;8N.)(-!=./.2F)/!K.)!N(('!-(H(2&M(-!/&!2.N(2!.;&3./,=!=&3M&B'-)!=&'/.,','Z!)B,/.N2(!-,;(=/,'Z!Z;&BM)#!OK(!;(.=/,&')!=.;;,(-!&B/!./!.3N,('/!/(3M(;./B;(!a,/K!>$!K.H(!N(('!(+M2&;(-!a,/K!)BN)/,/B/(-!.=(/&MK('&'()d!$8MK('F2MF;,-,'(d!N('G.',2,-(d!#+#8-,3(/KF2N('G.3,-(!.'-!IdP8N('G&xB,'&2,'(#$XP!>(B/(;./,&'!&7!=.;N&'F2!=&3M&B'-)!B),'Z!MF;;&2,-,'(!.)!.'!&;Z.'&=./.2F)/!,'!/K(!M;()('=(!&7!>$*!K.)!N(('!-()=;,N(-!NF!vK.'!*.-&8#$XR!>(B/(;,B3!,'=&;M&;./,&')!BM!/&!RRh!.'-!7B'=/,&'.2!Z;&BM!/&2(;.N,2,/F!.Z.,')/!8[*$d!8*E65d!8[CE65D$d!8U;d!8E**6d!8[6$!a.)!&N)(;H(-!a,/K!/K,)!3(/K&-&2&ZF#!T/&!*.-&8#$"X!;(M&;/(-!-(B/(;./,H(!=F=2,G./,&'!;(.=/,&')!&7!)B27.'F2!"d@8-,F'()!/&!7&;3!#8!.'-!E8=&'/.,','Z!K(/(;&=F=2()!C7B;.')!.'-!MF;;&2()D!B),'Z![.U>0!.'-!(/K.'&2#!?!;.'Z(!&7!)BN)/,/B/(-!7B;.')!.'-!MF;;&2()!a(;(!-(B/(;./(-!B),'Z!/K,)!3(/K&-!a,/K!"XXh!-(B/(;,B3!,'=&;M&;./,&'!,'!=(;/.,'!=.)()!C/D>%K%&LAD#! 38 !/D>%K%&LA5!>(B/(;./,H(!EF=2,G./,&'!/&!>(H(2&M!>(B/(;./(-!6(/(;&=F=2()!!A5O!/CKK"@P&OK,)!=K.M/(;!&B/2,'()!H.;,&B)!B)()!&7!-(B/(;,B382.N(2(-!=&3M&B'-)!.)!M;&N()!/&!B'-(;)/.'-!;(.=/,&'!3(=K.',)3)d!.)!/;.=(;)!,'!3(/.N&2,)3!)/B-,()d!.'-!.)!3(-,=,'.2!.Z('/)#!OK(!.N,2,/F!&7!-(B/(;,B3!/&!.2/(;!/K(!3(/.N&2,=!.'-!MK.;3.=&^,'(/,=!M;&7,2(!&7!.!-;BZ!,)!B)(-!(+/('),H(2F!'&a.-.F)!/&!-(H(2&M!'(a!/K(;.M(B/,=!.Z('/)!&;!/()/!/K(!-(B/(;./(-!.'.2&ZB()!&7!-;BZ)!,'!/K(!M,M(2,'(!/&!M;&/(=/!M./('/)#!OK,)!.MM2,=./,&'!;(M;()('/)!.'!),Z',7,=.'/!'((-!7&;!M&)/8)F'/K(/,=!6Y>!(+=K.'Z(!3(/K&-)!.MM2,=.N2(!&'!.!2.;Z(!)=.2(#!OK(!/K;((!/;.-,/,&'.2!3(/K&-)!&7!,'/;&-B=,'Z!-(B/(;,B3!K.H(!N(('!-,)=B))(-!,'!/K,)!=K.M/(;L!C"D!!"8-(M('-('/!6Y>!(+=K.'Z(r!C$D!6Y>!(+=K.'Z(!B'-(;!KF-;&/K(;3.2!&;!)BM(;=;,/,=.2!=&'-,/,&')r!.'-!C5D!/;.'),/,&'83(/.2!=./.2FG(-!6Y>!(+=K.'Z(#!OK(!6Y>!(+=K.'Z(!B'-(;!.=,-,=!&;!N.),=!=&'-,/,&')!=.'!.=K,(H(!K,ZK!-(B/(;,B3!,'=&;M&;./,&'!NB/!,)!'&/!.MM;&M;,./(!7&;!.=,-!&;!N.)(82.N,2(!)BN)/;./()r!KF-;&/K(;3.2!&;!)BM(;=;,/,=.2!3(/K&-)d!,'!/B;'d!=.'!N(!(77(=/,H(d!NB/!&'2F!7&;!/K(;3.22F!)/.N2(!)BN)/;./()!/K./!=.'!a,/K)/.'-!)B=K!.ZZ;()),H(!=&'-,/,&')#!OK(!Z('(;.22F!3,2-(;!/;.'),/,&'83(/.2!=./.2FG(-!6Y>!(+=K.'Z(!,)!3&)/!=&33&'2F!B)(-!NB/!/K(!.H.,2.N2(!,'=2B-(!.!7(a!-;.aN.=^)#!6(/(;&Z('(&B)!=./.2F),)!,)!M;(7(;;(-!./!/K(!,'-B)/;,.2!2(H(2!-B(!/&!/K(!(.)(!&7!=./.2F)/!;(3&H.2!.'-!M;&-B=/!,)&2./,&'!NB/!=B;;('/2F!.H.,2.N2(!K(/(;&Z('(&B)!/;.'),/,&'83(/.2!=./.2FG(-!6Y>!(+=K.'Z(!;(xB,;()!/K(!B)(!&7!6$!&;!>$!Z.)!.'-!&7/('!),Z',7,=.'/!M;())B;()!/&!-,))&2H(!/K()(!Z.)()#!SPhXRNaBD4DBU, EtOH, rt or reflux0.25-0.5 hXHHHRDX = O or NPhSR = H, Ph, Et 39 A5R!8'"$&'(&+>6,&:%,%"@D>&S@'T%D+&J&)/!&7!/K(!=B;;('/!6Y>!(+=K.'Z(!3(/K&-)!/K./!.;(!)(2(=/,H(d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r!C$D!,'(+M('),H(r!C5D!.xB(&B)8N.)(-r!C0D!)(2(=/,H(!.'-!C4D![&!6$!&;!>$!Z.)#!!m,/K!/K(!Z&.2!&7!,'=&;M&;./,'Z!/K()(!M;,'=,M2()d!a(!M;()('/!,'!/K,)!-,))(;/./,&'!.!K(/(;&Z('(&B)!/;.'),/,&'83(/.2!N.)(-!(2(=/;&=./.2F/,=!)F)/(3!a,/K!/K(!.N,2,/F!/&!.=/,H./(!E86!),/()!,'!&;Z.',=!3&2(=B2()!.'-!,'/;&-B=(!-(B/(;,B3!,'!.!;(Z,&)(2(=/,H(!.'-!)/(;(&;(/('/,H(!3.''(;#!T'!/K(!7&22&a,'Z!=K.M/(;)d!a(!a,22!-,)=B))!/K(!-(H(2&M3('/!&7!&B;!(2(=/;&=./.2F/,=!)F)/(3!/K./!.--;())()!.22!/K()(!Z&.2)!aK,2(!Z,H,'Z!K,ZK!-(B/(;,B3!,'=&;M&;./,&')#!!&!!!!!!!!!!! 40 )>"?+%@&J5&/+%@%'@%+%*+6=%&;FG&47D>"*H%&=6"&"*&4$%D+@'"D+6="+%B&;%+%@'H%*%'C,&)"+"$P,+&"+&,?M&)U;&/6+%,&3%"@6*H&2K6*%,&'@&2$D'>'$,&!J5A!.*+@'BCD+6'*&*B;!;()(.;=K!Z;&BM!K.)!7&=B)(-!&'!/K(!-(H(2&M3('/!&7!)/;./(Z,()!/&!=&'H(;/!,'(+M('),H(!)BN)/;./()!/&!H.2B.N2(!M;&-B=/)#!*'(!&7!/K(!M;,3.;F!/.;Z(/)!K.)!N(('!=&'H(;),&'!&7!2.=/,=!.=,-#!*H(;!/K(!2.)/!/a&!-(=.-()d!&B;!;()(.;=K!Z;&BM!K.)!(+.3,'(-!a.F)!/&!=&'H(;/!2.=/,=!.=,-!/&!.=;F2,=!.=,-d!.'-!2./(;!/&!$d58NB/.'(-,&'(!&H(;!MK&)MK./(d$""!)&-,B3d$"$d$"5!&;!.33&',B3!).2/)#$"0!T'!^((M,'Z!a,/K!/K(!&'Z&,'Z!7&=B)!&'!-(H(2&M3('/!&7!M./K)!/&!H.2B.N2(!M;&-B=/)d!vK.'Z!*.-&8#$"4d$"@!)/B-,(-!/K(!<BYE8=./.2FG(-!)F)/(3!&7!KF-;&Z('./,'Z!2.=/,=!.=,-!/&!M;&-B=(!M;&MF2('(!Z2F=&2d!.!=&33&-,/F!=K(3,=.2#!OK,)!;(.=/,&'d!=&'-B=/(-!./!"4X!eE!.'-!$"XX!M),!6$d!M;&-B=(-!M;&MF2('(!Z2F=&2!a,/K!PIh!=&'H(;),&'!CRXh!F,(2-D!,'!4!K#!OK,)!&N)(;H./,&'!a.)!7&22&a(-!NF!/K(!a&;^!&7!%(;(!*.-&8#"@Xd$"I!aK&!-(3&')/;./(-!/K(!KF-;&Z('./,&'!&7!98.2.','(!/&!98.2.','&2!a,/K!R5h!=&'H(;),&'!CR"h!F,(2-D!./!"XX!eE!.'-!"XXX!M),!6$!,'!@!K!C/D>%K%&LJD#!!/D>%K%&LJ5!6F-;&Z('./,&'!&7!E.;N&+F2,=!?=,-!>(;,H./,H()!!O&!M;&N(!/K(!3(=K.',)3!&7!KF-;&Z('./,&'!&7!98.2.','(!.'-!/K(!;(/('/,&'!&7!)/(;(&=K(3,)/;F!,'!98.2.','&2d!%(;(!*.-&8#"@X!M(;7&;3(-!6Y>!(+=K.'Z(!)/B-,()#!?/!"4X!eE!.'-!OHOOHOHOH0.5 g Ru/C150 ¡C 2100 psi H2, 5 h87% conversionZhang, 2001OOH0.5 g Ru/C100 ¡C, 0.29 M H3PO4 1000 psi H2, 6 hNH2HOHNH2H93% conversion99.2% eeJere, 2002 41 "XXX!M),!6$d!/K(F!&N)(;H(-!6Y>!(+=K.'Z(!./!/K(!i!),/(!,'!98.2.','(!.'-!98.2.','&2!a,/K&B/!.'F!2&))!,'!&M/,=.2!MB;,/F!C/D>%K%&LMD#!!/D>%K%&LM5!V/(;(&;(/('/,H(!6Y>!1+=K.'Z(!,'!98.2.','(!.'-!98.2.','&2!!>B(!/&!/K(!2&a!)&2BN,2,/F!&7!6$!,'!a./(;d!K,ZK(;!M;())B;(!a.)!;(xB,;(-!,/)!=&'=('/;./,&'!,'!/K(!2,xB,-#!O&!.H&,-!/K(!B)(!&7!6$!.'-!K,ZK!M;())B;(!/&!-,))&2H(!,/d!>.2.H&F!*.-&8#$"P!-(H(2&M(-!(2(=/;&=./.2F/,=!KF-;&Z('./,&'!C1E6D!&7!2.=/,=!.=,-!/&!M;&MF2('(!Z2F=&2!.)!.!3,2-!.2/(;'./,H(!/&!/K(!/;.-,/,&'.2!/;.'),/,&'!3(/.28=./.2FG(-!K,ZK8M;())B;(!N./=K!;(.=/&;!KF-;&Z('./,&'!3(/K&-#!T'!/K,)!3(/K&-d!/K(!=.;N&+F2,=!.=,-!3&,(/F!,)!;(-B=(-!NF!<BYE!B),'Z!./&3,=!KF-;&Z('!7&;3(-!./!/K(!=./.2F/,=!=./K&-(!H,.!;(-B=/,&'!&7!M;&/&')!C6kD!Z('(;./(-!./!.'&-(#!OK(!1E6!(+M(;,3('/!a.)!=&'-B=/(-!./!.3N,('/!M;())B;(!B),'Z!2.=/,=!.=,-!.'-!.'!<WE!C;(/,=B2./(-!H,/;(&B)!=.;N&'D!(2(=/;&-(!)B77B)(-!a,/K!4h!a/#!<BYE!M&a-(;!=./.2F)/!)(;H,'Z!.)!/K(!=./K&-(d!aK,2(!A/!a,;(!a.)!/K(!.'&-(#!c),'Z!.!/a&8=&3M.;/3('/!C$8ED!=(22d!.'&-(!.'-!=./K&-(!=&3M.;/3('/)!a(;(!)(M.;./(-!NF!.!Z2.))!7;,/!M;(H('/,'Z!/K(!-,77B),&'!&7!Z.)(&B)!)M(=,()#!?/!IX!eE!.'-!"XX!3?d!B),'Z!X#X"!J!6E2!.)!.'!(2(=/;&2F/(d!PX#5h!2.=/.2-(KF-(!.'-!$#Rh!M;&MF2('(!Z2F=&2!a(;(!7&;3(-!,'!$"!K!C/D>%K%&LLD#!!/D>%K%&LL5!1E6!<(-B=/,&'!&7!9.=/,=!?=,-!!OHONH2H1 g Ru/C0.27 M H3PO4150 ¡C, 1000 psi D2D2O, 6 hOHONH2DOHNH2D+DD84% conversion99% ee78% yield99.7% eeOHOOHRVC/5% Ru/C (Cathode)Pt (Anode)70 ¡C, 100 mA0.01 M HCl, 21 hHOOHOHOH+80.3% yield2.9% yieldDalavoy, 2007 42 ?!'(a!;()(.;=K!KFM&/K(),)d!/K./!/;.'),/,&'83(/.2!=./.2FG(-!;(.=/,&'!,'!K,ZK8M;())B;(!N./=K!;(.=/&;!=.'!N(!;(M2,=./(-!,'!.'!(2(=/;&=K(3,=.2!)(//,'Zd!(3(;Z(-!7;&3!/K(!7,'-,'Z)!&7!/K(!)/B-,()!3('/,&'(-!.N&H(#!J&)/!,3M&;/.'/!a(;(!/K(!7&22&a,'Z!/K;((L!.D!KF-;&Z('./,&'!&7!2.=/,=!.=,-!/&!M;&MF2('(!Z2F=&2d!=./.2FG(-!NF!<BYE!M&a-(;!=./.2F)/!.)!-(3&')/;./(-!NF!vK.'Z!*.-&8#!,'!K,ZK8M;())B;(!K,ZK8/(3M(;./B;(!N./=K!.'-!=&'/,'B&B)!;(.=/&;)r!ND!)/(;(&;(/('/,H(!6Y>!(+=K.'Z(!./!/K(!.3,'(8N(.;,'Z!)M5!E86!),/(!,'!98.2.','(!NF!%(;(!*.-&8#r!.'-!=D!(2(=/;&=./.2F/,=!KF-;&Z('./,&'!&7!2.=/,=!.=,-!NF!>.2.H&F!*.-&8B!,'!.!N('=K/&M!(2(=/;&=K(3,=.2!=(22!&NH,./,'Z!/K(!'((-!7&;!M;())B;(!&;!(+/(;'.2!)BMM2F!&7!6$#!O.^('!/&Z(/K(;d!/K()(!;()B2/)!)BZZ()/(-!/K./!/K(!(2(=/;&=./.2F/,=!=&'/(+/!)K&B2-!N(!=.M.N2(!&7!(77(=/,'Z!6Y>!(+=K.'Z(!./!),/()!2,^(!/K&)(!.=/,H./(-!,'!%(;(g)!)/B-,()#!m(!/K(;(7&;(!-(H(2&M(-!.!K(/(;&Z('(&B)!.MM;&.=K!/K./!a.)!3,2-d!Z;(('d!,'(+M('),H(d!;(Z,&)(2(=/,H(!.'-!)/(;(&;(/('/,H(!,'!E86!/&!E8>!=&'H(;),&'#!OK(!/;.')7&;3./,&'!a.)!=.;;,(-!&B/!,'!.!$8E!=(22!)(M.;./(-!NF!.![.7,&'}!3(3N;.'(!aK(;(!;(M2.=(3('/!&7!.!KF-;&Z('!./&3!a,/K!.!-(B/(;,B3!./&3!&'!/K(!&;Z.',=!)BN)/;./(!a.)!(77(=/(-!NF!;B/K(',B3!&'!.=/,H./(-!=.;N&'!=2&/K!C<BY?EEDd!.!)BMM&;/!&M/,3,G(-!NF!9,!*.-&8#$"R!/&!-(M&),/!;B/K(',B3#!?!A/!a,;(!)(;H(-!.)!.!=&B'/(;!(2(=/;&-(!.'-!/K(!(2(=/;&2F/(!B)(-!,'!/K(!)F)/(3!a.)!X#X"!J!MK&)MK./(!NB77(;!CM6!ID!M;(M.;(-!,'!>$*!/K./!M;&H,-(-!/K(!,&')!7&;!/K(!=&'-B=/,&'!&7!=B;;('/!.'-!)(;H(-!/K(!)&B;=(!&7!-(B/(;,B3#!OK(!;()B2/)!-()=;,N(-!K(;(!;(H(.2!/K(!=.M.N,2,/F!&7!K(/(;&Z('(&B)!<BY?EE!/&!.=/,H./(!E86!N&'-)!i!/&!K(/(;&./&3!C[!&;!*D!a,/K!&'2F!.!3&-()/!=B;;('/!-('),/F#!OK(!M;()('/!)/B-F!B)(-!>$*d!.'-!NFM.))(-!/K(!K,ZK8M;())B;(!=&'-,/,&')!.'-!(xB,M3('/!'((-(-!/&!-,))&2H(!/K(!M&&;2F!)&2BN2(!>$!C&;!6$D!,'!.'!.xB(&B)!('H,;&'3('/!./!=&'=('/;./,&')!(77(=/,H(!7&;!3.))!/;.')M&;/!.'-!-,))&=,./,&'!&'!/K(!=./.2F)/!)B;7.=(#!! 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!!!16HC@%&AL5!<(.=/,H,/F!&7!8*6!$%#!8[6$#!E&'-,/,&')L!VBN)/;./(!C$X!3J!,'!$X!39Dd!$#$!3?Y=3$!]!IX!eE!COMDYI4!eE!CORD#!T'!45d!j8E65g)!.;(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(C)D!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!T'!4@d!f8E65!.;(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(C)D!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!OK(!=K(3&)(2(=/,H,/F!,'!7.H&;!&7!.2=&K&2)d!.'-!/K(!,'.N,2,/F!&7!(/K(;(.2!Z;&BM)!/&!('.N2(!6Y>!(+=K.'Z(!a.)!7B;/K(;!(+M2&;(-!NF!.'.2FG,'Z!N&'-!)/;('Z/K)!B),'Z!&'-,0,.,2!3(/K&-)#!O&!/K,)!('-d!xB.'/B3!=K(3,=.2!=.2=B2./,&')!B),'Z!/K(!_5!3(/K&-$$0!a(;(!;B'!&'!,)&M;&MF2!.2=&K&2d!,)&M;&MF2!(/K(;d!,)&M;&MF2!.3,'(d!,)&M;&MF2!3(/KF2!.3,'(d!.'-!,)&M;&MF2!-,3(/KF2!.3,'(#!O&!=&'),-(;!.!;.'Z(!&7!N(K.H,&;)d!.22!/K(!B'=./.2FG(-!N&'-!=2(.H.Z()!a(;(!3&-(2(-d!,'=2B-,'Z!KF-;,-(d!KF-;&Z('!./&3d!.'-!M;&/&'!.N)/;.=/,&'!./!/K(!)(=&'-.;F!E86!),/()!i!/&!/K(![8!&;!*8K(/(;&./&3#!T'!/K(!=.)()!&7!-(M;&/&'./,&'!.'-!K&3&2F/,=!E86!=2(.H.Z(d!/K(!H.2B()!a(;(!a(.^2F!)('),/,H(!/&!K(/(;&./&3!,-('/,/F!C*!&;![D!.'-!/&!/K(!.2^F2!)BN)/,/B('/)!&'!/K(!K(/(;&./&3#!OK(!('(;Z,()!7&;!KF-;&Z('!./&3!;(3&H.2!H.;,(-!&H(;!.!;.'Z(!&7!•$#4!^=.2Y3&2d!OOHHOH2NDD56HONH2DDDD53X$X0X@XPX"XXX@X"$X"PX$0X5XX5@X0$X0PX40Xa&;PB@'H%*"_K6*`C8[6$D!C[&8E**6D!C8*6D!C[&8E**6D!C8*6D!C8[6$D! 58 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59 T'!/K(!(2(=/;&=K(3,=.2!.MM.;./B)d!98.2.','(!OL!C16HC@%&AOD!./!I4!‡E!)K&a(-!RPh!-(B/(;,B3!,'=&;M&;./,&'!,'!4!K!a,/K!'&!&N)(;H.N2(!;.=(3,G./,&'#!OK&BZK!)2&a(;d!98H.2,'(!OO!C16HC@%&AOD!.=K,(H(-!R5h!-(B/(;,B3!,'=&;M&;./,&'!,'!R!Kd!.'-!RRh!.7/(;!$"!Kd!.Z.,'!a,/K!=&3M2(/(!)/(;(&=K(3,=.2!;(/('/,&'#!m(!.//;,NB/(!/K(!)2&a(;!;./(!&7!98H.2,'(!$%B!98.2.','(!-(B/(;./,&'!/&!)/(;,=!=;&a-,'Z!./!/K(!;(.=/,H(!),/(d!=&'),)/('/!a,/K!&B;!(.;2,(;!)/B-,()!&7!.3,'&!.=,-!KF-;&Z('./,&')!/&!.3,'&!.2=&K&2)$$P!NB/!,'!.MM.;('/!=&'/;.)/!/&!/K(!.N&H(!;()B2/)!a,/K!),3M2(!.3,'()!LJULL#!! 60 !16HC@%&AO5!VBN)/;./(!V=&M(!C&IX!eEd!'I4eEd!(M6!"$d!)"!Z!)BN)/;./(d!*PXeED#!E&'-,/,&')L!VBN)/;./(!C$X!3J!,'!$X!39D!]!$#$!3?Y=3$#!!m,/K!N&/K!.3,'(!.'-!.2=&K&2qN(.;,'Z!)/(;(&=('/(;)d!98/K;(&','(!OR!a.)!&7!M.;/,=B2.;!,'/(;()/#!?7/(;!R!Kd!sP4h!-(B/(;./,&'!a.)!&N)(;H(-!./!N&/K!),/()d!.'-!sRRh!,'!$"!K!a,/K!)/(;(&=K(3,=.2!;(/('/,&'!./!N&/K!)/(;(&=('/(;)#!T'/(;()/,'Z2Fd!/K(!;./(!&7!.=/,H./,&'!&7!),/()!i!/&!KF-;&+F!C10;!u!5#R+"X85!)8"!$%#!1\;J!u!5#X+"X85!)8"D!a.)!'&/!&N)(;H(-!/&!N(!),Z',7,=.'/2F!NH2DHNDCD3NDCD3D3CNDDDDNH2D46 (8 h, 92%)42 (5 h, 97%)43 (5 h, 95% & 95%)44 (5 h, 93% & 97%)45 (5 h, 74% & 68%)OHDOHD47 (8 h, 87%)48 (4 h, 93%)DHO49 (2.5 h, 92%, 27%)DHOOCH350 (3 h, 93%, 53%)DHOCOOH51 (24 h, 75%)DHODOHHOD52 (24 h, 70%)OOHNH2DOOHNH2DOOHHOH2NDD54 (5 h, 98%)b55 (8 h, 93%)b56 (9 h, 90% & 86%)bHONH2DDDD53 (9 h, 94% & 33%)acN57 (No Deuteration)NDDDD58 (10 h, 88%)eDDOHD48 (53 h, 87%)d 61 7.)/(;!.)!,/!a.)!,'!/K(!=.)(!&7!OMr!a(!.//;,NB/(!/K,)!/&!M&)),N2(!ZB,-.'=(!NF!/K(!=.;N&+F2./(!Z;&BM!,'!98/K;(&','(!C16HC@%&ALD#!!$#5#0!E./.2F)/!>(.=/,H./,&'!V/B-,()!177(=/,H(!=./.2F)/!2,7(/,3(!,)!.!^(F!7.=/&;!-(/(;3,','Z!/K(!M;.=/,=.2!H.2B(!&7!.'F!=./.2F/,=!)F)/(3#!O&!M;&N(!/K(!(+/('/!&7!-(.=/,H./,&'d!a(!;(B)(-!/K(!<BY?EE!=./K&-(!7&;!7,H(!=&')(=B/,H(!;B')!a,/K!.2.','(!C;.=(3,=D!.)!/K(!)BN)/;./(#!?7/(;!/K(!7,;)/!=F=2(d!B)(-!<BY?EE!=./K&-(!a.)!a.)K(-!a,/K!4!39!&7!>$*!.'-!-;,(-!&H(;',ZK/!B'-(;![$#!9(H(2)!&7!-(B/(;,B3!,'=&;M&;./,&'!a(;(!=&3M.;.N2(!/K;&BZK&B/!.22!/K(!;B')d!-(3&')/;./,'Z!/K(!)/.N,2,/F!&7!/K(!<BY?EE!=./.2F)/#!OK(!=./.2F)/!a.)!)BN)(xB('/2F!B)(-!7&;!/K(!),+/K!/,3(!a,/K!H.2,'(!C;.=(3,=D!/&!/()/!7&;!=;&))8=&'/.3,'./,&'!.'-!7&;!=K.'Z()!,'!(77,=.=F!a,/K!.'&/K(;!)BN)/;./(#!OK(!;(.=/,&'!)K&a(-!R5h!-(B/(;,B3!,'=&;M&;./,&'!,'!P!Kd!=&3M.;.N2(!/&!/K(!;()B2/)!&N)(;H(-!a,/K!/K(!7;()K!<BY?EE!CR5h!,'!R!KD#&!!!!&! 62 !!16HC@%&AR5!E./.2F)/!>(.=/,H./,&'!V/B-,()#!E&'-,/,&')L!EF=2&M('/.'&2!C$X!3J!,'!$X!39Dd!$#$!3?Y=3$!]!@X!eE#!OK(!E6$g)!.;(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!$#5#4!177(=/!&7!EB;;('/!>('),/F!OK(!(77(=/!&7!=B;;('/!-('),/F!&'!/K(!(+/('/!.'-!;./(!&7!/K(!-(B/(;,B3!,'=&;M&;./,&'!a.)!.2)&!)/B-,(-!B),'Z!98H.2,'(!.)!)BN)/;./(!a,/K!=B;;('/!-('),/,()!;.'Z,'Z!7;&3!"#"!3?Y=3$!/&!""#"!3?Y=3$#!OK(!M;&y(=/(-!3.=;&)=&M,=!=2&/K!.;(.!&7!0#4+"X80!3$!a.)!B)(-!/&!=.2=B2./(!=B;;('/!-('),/,()d!.)!,/!a.)!-,77,=B2/!/&!3(.)B;(!/K(!.=/B.2!(77(=/,H(!(2(=/;&-(!)B;7.=(!.;(.#!OK(!Z&.2!a.)!/&!7,'-!.'!&M/,3B3!=B;;('/!-('),/F!/K./!=&B2-!&+,-,G(!>$*!/&!Z('(;./(!-(B/(;,B3!=./,&')!&'!A/d!.'-!;(-B=(!/K(3!&'!/K(!<B!)B;7.=(!C/D>%K%&LOd!4^*,5&Q!]!OD!NB/!/&!.H&,-!)./B;./,&'!&7!/K(!=./.2F/,=!),/()!2(.-,'Z!/&!/K(!>$!7&;3./,&'!C/D>%K%&LOd!1x')#!R!]!WD#!T'!/K()(!6Y>!(+=K.'Z(!;(.=/,&')d!.MM2,=./,&'!&7!=B;;('/!,)!'(=()).;F!7&;!/a&!;(.)&')L!C.D!;(-B=/,&'!&7!;B/K(',B3!/&!/K(!.=/,H(!)/./(!.'-!CND!;(-B=/,&'!&7!>k!&;!>$*!&'!/K(!;B/K(',B3!)B;7.=(!/&!Z('(;./(!<B!C>D!aK,2(!/K(!E86!.=/,H./,&'!)/(M!&7!&;Z.',=!)BN)/;./()!/&!(77(=/!6Y>!(+=K.'Z(!-,-!'&/!'((-!.'F!(2(=/;&')#!OK,)!.)M(=/!&7!&B;!=K(3,)/;F!a&B2-!;('-(;!&B;!;(.=/,&')!K,ZK!=B;;('/!(77,=,('=F!.)!2,3,/(-!=K.;Z(!,)!;(xB,;(-!/&!-;,H(!/K()(!;(.=/,&')#!X$X0X@XPX"XXX@X"$X"PX$0X5XXa&;PB@'H%*"_K6*`h!6F-;&Z('!C")/!<B'Dh!6F-;&Z('!C$'-!<B'Dh!6F-;&Z('!C5;-!<B'Dh!6F-;&Z('!C0/K!<B'Dh!6F-;&Z('!C4/K!<B'D 63 OK(&;(/,=.22Fd!(2(=/;&')!)BMM2,(-!,'!/K(!6Y>!(+=K.'Z(!;(.=/,&')!a(;(!&'2F!;()M&'),N2(!7&;!/K(!Z('(;./,&'!&7!>$!.'-!a&B2-!M;&H,-(!;(2./,H(2F!K,ZK(;!=B;;('/!(77,=,('=,()#!!!/D>%K%&LO5!12(=/;&=K(3,=.2!<(.=/,&')!./!E./K&-(!.'-!?'&-(!!U.)(-!&'!M;(2,3,'.;F!.'.2F),)d!$#$!3?Y=3$!a.)!.'!(77(=/,H(!=B;;('/!-('),/F!7&;!/K(!M;(8(2(=/;&2F),)!.=/,H./,&'!MK.)(!&7!5X!3,'B/()#!?7/(;!M;(8(2(=/;&2F),)d!;(.=/,&')!a(;(!;B'!./!X#0!3?Y=3$d!"#"!3?Y=3$d!$#$!3?Y=3$!.'-!""#"!3?Y=3$r!"#"!3?Y=3$!/B;'(-!&B/!/&!N(!/K(!3&)/!(77(=/,H(!,'!3.,'/.,','Z!.!N.2.'=(!N(/a(('!/K(!7.H&;.N2(!C&+,-./,&'!.'-!;(-B=/,&'D!.'-!B'7.H&;.N2(!C>$!-()&;M/,&'D!)/(M)#!T'/(;()/,'Z2Fd!/K(!)2&a(;!6Y>!(+=K.'Z(!;./()!7&B'-!./!K,ZK(;!=B;;('/!-('),/F!)BZZ()/!/K./!>$!-()&;M/,&'!M;&=())()!&;!-(B/(;&+,-(!.',&')!3.F!/,(!BM!.=/,H(!),/()!H,.!)B;7.=(!)./B;./,&'d!M.;/,.22F!,'K,N,/,'Z!;(.=/,&'#![&/.N2Fd!,'!.22!/K()(!(+M(;,3('/)d!/K(!)/(;(&=K(3,)/;F!&7!98H.2,'(!a.)!=&3M2(/(2F!;(/.,'(-#!Formation of Ru(D)2Ru2D2O2e-2Ru(D)+2ODD2+Ru2OD+D2 DesorptionRu(D)e-D2OD2+2RuRu(D)Ru(D)Eqn.6Eqn.7Eqn.8CATHODE (Ru/ACC)ANODE (Pt)O2+4D+(aq)Pt2D2O+4e-Eqn.9Oxidation of D2Oe- RuD+Ru(D)Eqn.5 64 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&!16HC@%&ML5!"6![J<!)M(=/;B3!&7!EF=2&K(+F2.3,'(d!0@!C\,(2-!C0"hDD#!EK.'Z()!,'!=K(3,=.2!)K,7/)!.;(!-B(!/&!/K(!=K.'Z(!,'!M6!;()B2/,'Z!7;&3!(2(=/;&=K(3,=.2!=&')B3M/,&'!&7!>k!,&')#!OK(!E6$g)!.;(!/K(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!&&&&&&&&PB pH 7 (D2O)10 mA, 60 oC       (20 mM)Ru/ACC (cathode) Pt (anode)abNH2HND2DaabbAt 0 hAfter 8 h 82 &!16HC@%&MO5!"6![J<!)M(=/;B3!&7!58M('/.'&2d!0I!C\,(2-!C"@hDD#!EK.'Z()!,'!=K(3,=.2!)K,7/)!.;(!-B(!/&!/K(!=K.'Z(!,'!M6!;()B2/,'Z!7;&3!(2(=/;&=K(3,=.2!=&')B3M/,&'!&7!>k!,&')#!OK(!f8E6$g)!.'-!j8E65g)!.;(!/K(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!!!!!!!!!!!!!!OHHODD20 mMPB pH 7 (D2O)10 mA, 60 oCRu/ACC (cathode) Pt (anode)baccb 83 &!16HC@%&MR5!"6![J<!)M(=/;B3!&7!EF=2&M('/.'&2d!0P!C\,(2-!C00hDD#!EK.'Z()!,'!=K(3,=.2!)K,7/)!.;(!-B(!/&!/K(!=K.'Z(!,'!M6!;()B2/,'Z!7;&3!(2(=/;&=K(3,=.2!=&')B3M/,&'!&7!>k!,&')#!OK(!E6$g)!.;(!/K(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!!!!!!!!!!!!!!20 mMPB pH 7 (D2O)10 mA, 60 oCRu/ACC (cathode) Pt (anode)abHOHDOD 84 &!16HC@%&MW5!"6![J<!)M(=/;B3!&7!083(/KF2=F=2&K(+.'8"8&2!C(,%-k!./&0%Dd!0R!C\,(2-!C$IhDD#!EK.'Z()!,'!=K(3,=.2!)K,7/)!.;(!-B(!/&!/K(!=K.'Z(!,'!M6!;()B2/,'Z!7;&3!(2(=/;&=K(3,=.2!=&')B3M/,&'!&7!>k!,&')#!OK(!E6$g)!.;(!/K(!'&'82.N,2(!KF-;&Z(')!.'-!h!KF-;&Z('!./!/K(!i!E86!),/(!,)!=.2=B2./(-!;(2./,H(!/&!/K(3#!!!20 mMPB pH 7 (D2O)10 mA, 60 oCRu/ACC (cathode) Pt (anode)abcHOHHCH3DODDCH3daaccddbbAt 0 hAfter 4 h 85 !!16HC@%&MQ5!S,'(/,=!?'.2F),)L!083(/KF2=F=2&+.'8"8&2!.'-!?=(/,=!?=,-!!!!!!!!!!!!!!!!!!!!!!!!!!F!u!8X#XX"$+!k!0#@"50<…!u!X#R05I5A<@=A<AA<A=A<=A<==A<BA<B=;?;A;B;C;>;;>?;>A;>B;$*b;#c"_,%D`$*b;#c 86 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