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O*JQ*\>HJ?>O*A?I*API>L=I>O*AN>*KPAOOCKAPP=*AKLC>M>I* FOC?E*L=INCI>OW*KAHAP=HCK* L=INJE>?AHCJ? W*A?I*C?*OJB>*KAO>O* GA\>N dO*=>AOHZ** '?*`jb]W*HL>*> P>KHNJKL>BCKAP* O=?HL>OCO*JQ* OJNGCHJP* A?I*B A??CHJP *QNJB*EPFKJO>*YAO*JQQCKCAPP=*DNAKHC K>I*G= *%HPAO* 2JYI>N*#JZ *C?*HL>*+?C H>I* (HAH>OZ *)L>* >P>KHNJKL>BCKAP*N>AKHJN*YAO*A?*JD>? XHJD*ICMCI>I*K>PP*QCHH>I*YCHL* A?*ABAPEABAH>I XP>AI*KAHLJI>* A?I*A*P>AI*A?JI>Z*)L>*KAHLJP =H>*YAO* A?*ARF>JFO*OJPFHCJ?*JQ*OJICFB*L=IN JaCI>*A?I*HL>*A?JP=H>* YAO*ICPFH>*OFPQFNCK* AKCIZ* '?*HL>* GAOCK*OJPFHCJ?*, XEPFKJO>*COJB>NCV>I*DANHCAPP=*HJ*BA??JO>*A?I*GJHL* ,XEPFKJO>*A?I*BA??JO>*Y>N>*N>IFK>I*HJ*OJNGCHJP*A?I*BA??CHJPZ &"****C6/&*%!4"2452 A,+:4P>KHCM>* >P>KHNJ N>IFKHCJ?*JQ* KANGJa=PCK*AKCI*HJ*API>L=I>*JN*APKJLJP *CO*A*KLAPP>?EC? E*DNJK>OOZ* (HNJ?E P=*N>IFKC?E*L=INCI>*N>AE> ?HO*OFKL*AO*/ C%P$ "*A?I*5$ #*AN>*BJO HP=*>BDPJ=>I*QJN*HL>*N>IFKHCJ?* JQ*KANGJa=PCK*AKCI*HJ*DNCBAN=*APKJLJPO*YL>N>AO* HL>*OD>KCAPCV>I*N>AE>?HO* ,'5%/ X$*CO*>BDPJ=>I*QJN *N>IFKHCJ?*HJ*API>L=I>Z*)LJFEL*&A5$ "*IJ>O*?JH*N>IFK>*K ANGJa=PCK*AKCI O*F?I>N*ABGC>?H*KJ?ICHCJ?O W*2>NCAOAB=*>H* APZ*LAM>*N>DJNH>I*O>P >KHCM>*N>IFKHCJ?*YCHL*&A5$ "*A?I*' !*HJ*APKJLJPO Z*%*O>P>KHCM>* N>IFKHCJ?*JQ*KC??ABCK*AKCI*HJ*HL>*KJNN>ODJ?IC?E* !?OAHFNAH>I*APKJLJP*YAO*N>DJNH>IZ &.********!!-#*!"#$%&'() P)'B&=$67".0' .8'!"#$$0:37$%37&=' 63%<.A;4"6 '36"='7.' 344;4"6' 346.9.4 ''!.JNBAHCJ?*JQ*API>L=I>O* QNJB*KANGJa=PCK*AKCI*CO*LANI*HJ*AKLC>M>*GFH* 5NJJ\LANH*>H*AP Z*N>DJNHO*A*BJN>* AHHNAKHCM>*B>HLJI *C?*YLCKL *L=INJOCP=PAHCJ?*JQ* A*KANGJa=PCK*AKCI* JKKFNO *YCHL*HL>*ACI*JQ*A*/>YCO*AKCI* 56#..7#*HJ*QJNB *A*ICOCP=P*AK>HAP*YLCKL*CO*>AOCP=*KJ?M>NH>I*HJ*API>L=I>*G=*AKCI*L=INJP=OCOZ &0****'!"#$%&'() Q)'R&4&67"S&'%&=$67".0'.8'63%<.A;4"6'36"='7.'34=&9;=& ''!!OOHOHNaBH 4 (1.2 eq.), I 2 (0.5 eq.) 0 ¡C, 97%NaBH 4 + RCOOH RCOOBH 3Na + H 20.5 I2RCH2OBO RCOOBH 2 + 0.5 NaI + 0.5 H 2OOHPh3SiH (2.3 eq.), B(C 6F5)3 (0.1 mol%) 15 h, 23 ¡C, >99% OSiPh 3OSiPh 3TBAF, H 2OOH!!%.#D96*%+4+6/&*%!4"2452=+4@,%!*2 A,+:4KHNJP=HCK*N>IFKHCJ?* JQ*ANJBAHCK*AKCIO* LAO*G>>?*OHFIC>I*F?I>N*AHBJODL>NCK*DN> OOFN>*A? I*C?*JD>?* M>OO>POZ*#AN P*!>HHP>N*C?*`jU^*I>BJ?OHNAH>I*HL>*>P>KHNJN>IFKHCJ?*JQ *G>?VJCK*AKCI*HJ*G>?V=P*APKJLJP* C?*ARF>JFO* APKJLJPCK* OFPQFNCK*AKCI *AH*hX`T*%BkKB !*J?*P>AI*>P>KHNJI> O*AH*TU XbU*_# *A?I*=C>PI>I*]U XjUr*DNJIFKHZ *&+*(H>C?*>H*APZ*APOJ*I>BJ?OHNAH>I* OCBCPAN* O>P>KHCM>*>P>KHNJN>IFKHCJ?*JQ*G>?VJCK*AKCI*HJ* G>?V=P*APKJLJP*YCHL*TUr*OFPQFNCK*AKCI*C?*>HLA?JP*YCHL*f XTU*%BkKB !*J?*K=PC?INCKAP* P>AI*>P>KHNJI>O *AH*b U_#*A?I*LAI*JM>N* iUr*=C>PIO Z&'*2N>OFBAGP>* A?*!"#$!%&*QJNB>I* >OH>N*C?H>NB>ICAH>*CO* BJN>* OFOK>DHC GP>*HJ *>P>KHNJ N>IFKHCJ?* HLA?*A*DPAC?*KANGJa=PCK*AKCI Z*$JY>M>NW*AH*HLAH*AKCI*KJ?K>?HNAHCJ?W* HL>*0 X#--$*CO*DNJHJ?AH>IW*OJ*BA=*G>*EJJI*AH*AKK>DHC?E* A?*>P>KHNJ?* QNJB* 2GW*YLCKL *CO*GAI*AH* N>IFKC?E*DNJHJ?O*HJ*BA\>* $!Z** *!2!!"#$%&'() T)'R&4&67"S&'&4&67%.63734;7"6'%&= $67".0'.8'<&0U."6'36"='7.'<&0U;4'346.9.4 '*(>P>KHCM>*>P>KHNJN>IFKHCJ?*JQ*G>?VJCK*AKCI *A?I*OAPCK=PCK*AKCI *HJ*G>?VAPI>L=I> *A?I*OAPCK=PA PI>L=I>* N>OD>KHCM>P= *LAM>*G>>?*OHFIC>I*YCHL*B>NKFN=* KAHLJI> O*AO*Y>PPZ *)L>* >P>KHNJP=H> O*FO>I*L >N>*Y>N>* GJNCK*AKCI*A?I*OJICFB*KANGJ?AH>*OJPFHCJ?*YCHL* LJH* G>?V>?>*JN*HJPF >?> *AO*A*KJ*OJPM>?HZ* +OC?E*G>?V>?>* AO*KJ XOJPM>?H* N>BJM>I*HL> *API>L=I>*QNJ B*HL>*ARF>JFO*OJPFHCJ?* HJ*DN>M>?H*CH O*QFNHL>N*KJ?M>NOCJ?* HJ* HL>*APKJLJP Z*'H*YAO*DNJDJO>I*HLAH*CH*YAO*HL>* QJNB AHCJ?*JQ*OJICFB*ABAPEAB *HLAH*KJ?M>NH>I*HL>*AKCI*HJ*API>L=I> Z&-,!/***OHOAnode and Cathode: Lead Electrolyte: alcohol + H 2SO4Temp¡ = ca. 30¡C Current density: 4-20 mA/cm 2OH!!%%#*!"#$%&'() (V)'I4&67%.63734;7"6'%&=$67".0 '.8'<&0U."6' 36"='30=':34"6;4"6'36"='7.'<&0U34=&9;=&' 30=':34"6;434=&9;=& '!"P>KHNJN>IFKHCJ?* JQ* ANJBAHCK*AKCI O*F?I>N*DN>OOFN CV>I*L=INJE>?*A?I*KANGJ ?*ICJaCI>* EAO>O*LAM>* APOJ*G>>?* >aDPJN>I W*C?M>OHCEAHC?E*HL>*>QQ>KH*JQ*DN>OOFN>*J?*HL>*>P>KHNJP=HCK*O=OH>BZ* )L>*N>AKHCJ? O*Y>N>*D>NQJNB>I*AH* h*%kIB !*YCHL*DN>OOFN>*JQ*` XbU*AHB*YCHL*H>BD>NAHFN>*B AC?HAC?>I*AH*^U_# *FOC?E*YAH>N*GAHLZ*'H *YAO*JGO>NM>I*HLAH *HL>*=C>PI*A?I *KFNN>?H*>QQCKC>?K=*C?KN>AO>I*YCHL* C?KN>AOC?E* DN>OOFN> Z*)LFOW *JM>N*HL>*NA?E>*JQ*` XbU*AHB* =C>PI>I*^U Xi`Zbr*A?I*KFNN>?H*>QQCKC>?K=* JQ*ffZhr*HJ* ]`Zfr*N>OD>KHCM>P=Z* 'H*YAO* JGO>NM>I*HLAH*HL>*EAO*FO>I*LAI* ?J*>QQ>KH*J?*HL>*=C>PI*A?I*#Z"*AH* `*AB* GFH*A*M>N=*OCE?CQCKA?H*>QQ>KH*J ?*HL>*N>OFPHO*AH*LCEL* DN>OOFN>OZ*.JN *C?OHA?K>W*C?ICMCIFAP*N>AKHCJ?O*AH*`* AHB*YCHL *$!*JN*#-!*EAM>*ffZhr*=C>PI* A?I*AH*bU*AHB* EAM>*]`Zfr*HJ*^fr* =C>PIO*N>OD>KHCM>P=Z*)L>* >QQ>KH*JQ*DN>OOFN>*YAO* APOJ*C?M>OHCEAH>I *QJN* >P>KHNJKL>BCKAP*KJ?M>NOCJ?*JQ* G>?VJCK*AKCI*HJ* G>?VAPI>L=I> Z*$>N>W *A*B>NKFN=*KAHLJI> *YAO*FO>I* C?*A*BCaHFN> *JQ* OFPQFNCK*AKCI*A?I*>HLA?JPZ* )L> *N>AKHCJ?*YAO*KJ?IFKH>I* AH*TU XT^*_# *AH*` XbU*AHB Z*(CBCPAN*HJ*HL>* >QQ>KH*JQ*DN>OOFN>* J?* HL>*G>?VJCK* AKCI*HJ*G>?V=P*APKJLJP*N>IFKHCJ?W* AH*`*AHB W*$!*JN*#-!W*=C>PI>I*`hZbr*>AKL* YCHL*#Z"*JQ* ]Zhr*YL>N>AO* AH*bU*AHB*fbr* *=C>PI*YAO*AKLC>M>I*YCHL*$!%A?I*J?P=* HNAK>* N>IFKHCJ?* YAO*JGO>NM>I*QJN*#- !Z*!&***********'!%+4 #*4@(4&"/$2!"P>KHNJKAHAP=HCK*N>IFKHCJ?*JQ*ANJBAHCK*?CHNJ*KJBDJF?IO*BA=*G>*HL>*BJOH*OHFIC> I*JNEA?CK* N>IFKHCJ?*DNJK>OOZ* "P>KHNJKL>BCKAP*O=?HL>OCO*JQ*RFC?JPJ?>*A?I*RFC?JaAPC?>* LAM>*G>>?*AKLC>M>I*J?* OHOAnode: Lead //Cathode:Mercury divided cell boric acid + Na 2CO3 / organic solvent Temp¡ = ca. 25-30¡C Current density: 6 A/cm 2HORR = H, OH R!!%�A?>=*&CK\>P*>P>KHNJI> O*MCA*C?HNABJP>KFPAN* ABCI>*QJNBAH CJ?*QNJB*HL>*L=INJa=PABC?>*QJNB>I* HLNJFEL*>P>KHNJL=INJE>?AHCJ?*JQ*HL>*KJNN>ODJ?IC?E*?CHNJ XKJBDJF?IO *G=*/>OOANI*>H*APZ!!*****!!!"#$%&'() (()'I4&67%.69&,"634':;07 9&:":'.8'N$"0.4.0& '(CBCPANP=W *HL>* >P>KHNJO=?HL>OCO*JQ *6>HL=P*fW^ XICL=INJXfXJaJX^XL=INJa= X`WTWfXHNCAVJPJ*|`W^ XA}*RFC?JaAPC?> XT*XKANGJa=PAH>7* YAO*AKLC>M>I*YCHL* i^rW*YL>N>AO*HL>*KPAOOCKAP*O=?HL >OCO*YAO*N>DJNH>I* HJ*LAM> *=C>PI>I*h^rZ !#**!!!"#$%&'()' (*)'I4&67%.69&,"634':;079&:":'.8'N$"0. A34"0& '!'!%+!96$ 2!)L>* >P>KHNJKL>BCKAP* N>IFKHCJ?*JQ*J NEA?CK*?CHNCP>O* C?*AKCICK* B>ICFB *ECM>O*ABC?>O*YL>N>AO*C?*AP\APC?>* JN*?>FHNAP*B>ICFB* HL>*#X#&*GJ?I*CO*KP>AM>IZ*$JY>M>N W*!W#XF?OAHFNAH>I*?CHNCP>*F?I>NEJ* >P>KHNJ L=INJICB>NCVAHCJ? *C?*A?*AP\APC?>*B>ICFB Z!"*)L>* >aH>?H *JQ*ICB>NCVAHCJ?*CO*AQQ>KH>I*G=*QAKHJNO* OFKL*AO*N>IFKHC J?*DJH>?HCAPOW*>P>KH NJ?CK*A?I*OH>NCK*>QQ>KHOZ *0>IFKHCJ?*YCHL*KJGAPH XGAO>I*BJP>KFPAN* >P>KHNJKAHAP=OCO* YAO*N>DJNH>I*HJ* KJ?M>NH*AK>HJ?CHNCP>*HJ*>HL=PABC?>Z* )YJ*KJGAPH*GCO XCBC?JD=NCIC?>OW* |#J6,,276$ !-7!}6&-#7!*6`W*,,2*p*KCO X|`WbXGCO6TXD=NCIC?=P>?ABC?>7}*K=KPJL>aA?>7*A?I*|#J6KCO XEtO 2CCO2EtNO24eÐ, 4H+Ð 2 H2OEtO 2CCO2EtNHOHÐ EtOH NOOHCO2EtQuinoloneNO2NNNCO2EtEtO 2C4eÐ, 4 M(H) Ð2 H2ONHOHNNNCO2EtEtO 2CNNNNCO2EtOHO!!%'#,,-276&-#7}6&-#7*6TW*KCO X,,-2*p* *!$ XbW^XGCO|6TX*2=NCIC?=P>?ABC? >}X%+,"$XL=INJa=K=KPJL>aA?>7 !.**Y>N>*>aDPJN>I*QJN*HL>CN*$"#O*DJH>?HCAP*A?I*LCEL*O>P>KHCMCH=*QJN*AK>HJ?CHNCP>**N>IFKHCJ?Z*%POJW*HL>* >P>KHNJKL>BCKAP *N>IFKHCJ?*JQ*AICDJ?CHNCP>*HJ*L>aAB>HL=P>?>ICABC?>*FOC?E*?CK\>P*>P>KHNJI>*LAO* G>>?*OHFIC>I**!*!"#$%&'()' (?)'+.<347'63734;:7 :'8.%'&4&67%.63734;:":'.8'0"7%"4&'%&=$6 7".0)'' '!E@!"620>IFKHCM>*ABC?AHCJ?* JN*N>IFKHCM>*AP\=PAHCJ?* N>AKHCJ? O*JQ*\>HJ?> O*JN*API>L=I> O*YCHL*ABC?> O*DNJK>>I*MCA* QJNBAHCJ?*JQ*A?* CBC?>*C?H>NB>ICAH>*YLCKL* CO*HL>? *N>IFK>I* G=*BCPI*N>IFKC ?E*AE>?HO*OFKL*AO* &A5$ ##&Z** "P>KHNJKAHAP=HCK*N>IFKHC M>*ABC?AHCJ? O*JQ*>P>KHNJ? XI>QCKC>?H*API>L=I> O*A?I*\>HJ?>O*LAM>*G>>?*I>M>PJD>I*G=*gLJF*>H*AP Z*YLCKL*Y>N>*ADDPC>I*HJ*HL>*O=?HL>OCO*JQ*6q7* KPJDCIJEN>PW* A*B>ICKAHCJ?*QJN*N>IFKC?E*HL>*NCO\*JQ*L>ANH*ICO>AO>*A?I*OHNJ\>*C?*DAHC>?HO*YCHL*LCEL* NCO\Z!0**!!%(#*!"#$%&'()' (H)'3W'@9&'7%3="7".03 4':;079&:":' 30='"=.#%&4 '!!ClCOOMe OClCOOMe NHNSSNaBH 3CNMeOH, pH = 4 +ClCOOMe OH+(±) Clopidogrel 28%61%ClCOOMe OHNS+ClCOOMe NSClCOOMe NSa) Syntheis of (±) Clopidogrel b) Electrolysis promoted reductive amination (±) Clopidogrel iminium cation Zn(OAc) 2 (0.1 M), HOAc/MeCN (1:10) Zn(+)/Ni(Ð), 8 mA, beaker-type cell (undivided cell) HClRoom temp. !!%)#6&;3/1&=&0*"+'" 8+))%3" >/$?+0"@%*4" #%+=/))" >/$?+0 "!.#'/%00) 1'(2+30#'()&')4,+50 )!,F>*HJ*HL>*?J? 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XICCOJDNJD= PABC?>*6$y?CEdO* GAO>7*C?*EJJI*=C>PIOZ*/JJ\C?E*AL>AIW*Y>*KJ?HC?F>*HJ*DFNOF>* BJN>*>QQ>KHCM>*YA=O*HJ*AP\=PAH>*ANJBAHCK*ABC?>OW*A?I*HJ*>a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`' "G,&79;4>;%%.4"="0&'/"79'TO`'6.0S&%:".0'X<.77.,W '!!NHHbHbHcHdHcHdHaHae'HNCH3Hb'Hb'Hc'Hd'Hc'Hd'Ha'Ha'HACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3OH (19:1) pH 7.0, 60 ¡C, 10 hH2O!!,(#'XB>HL=PD=NNJPCIC?>*YCHL*jhr*KJ?M>NOCJ?*6GJHHJB7Z* *!&$*&!03*0>AKHCJ?*JQ*D=NNJPCIC?>*YCHL*>HLA ?JP **""!"#$%&'?) T)'@9&'&0='%&367".0'.8'>;%%.4"="0&'X7.>W'/"79'&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&=' QT`' "G&79;4>;%%.4"="0&'/"79'T?`'6.0S&%:".0'X<.77.,W)' *"!!NHHbHbHcHdHcHdHaHae'HNCHb'Hb'Hc'Hd'Hc'Hd'Ha'Ha'HCH3f'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hHHH2O!!,)#&$*&!03*0>AKHCJ?*JQ*D=NNJPCIC?>*YCHL*COJDNJD=P*APKJLJP **""!"#$%&'?) (V)'@9&'&0 ='%&367".0'.8'>;%%.4"="0&'X7.>W'/"79'":.>%.>;4'346.9.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='OV`' "G&79;4>;%%.4"="0&'/"79'TM`'6.0S&%:".0'X<.77.,W) '"!!NHHbHbHcHdHcHdHaHae'HNCHb'Hb'Hc'Hd'Hc'Hd'Ha'Ha'HCH3f'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/( CH3)CH OH (19:1) pH 8.5, 60 ¡C, 10 hHCH3H2O!!,*#&$*&!03*0>AKHCJ?*JQ*BJNDLJPC?>*YCHL*B>HLA?JP **"!"#$%&' ?)(()'@9&'%&367".0' .8',.%>9.4"0&'X7.>W'/"79',&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='OQ`' CG,&79;4,.%>9.4"0&'/"79'QP`'6.0S&%:".0'X<.77.,W) '!!NHHbHbHcHdHcHdHaHae'HCH3ONHbHbHcHdHcHdHaHaHOACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3OH (19:1) pH 7.0, 60 ¡C, 10 hH2O!!,+#&$&!03*0>AKHCJ?*JQ*BJNDLJPC?>*YCHL*>HLA?JP **"!"#$%&'?) (*)'@9&'%&367".0'.8',.% >9.4"0&'X7.>W'/"7 9'& 7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='OT`' "G&79;4,.%>9.4"0&'/"79'TQ`'6.0S&%:".0'X<.77.,W) '!!NHHbHbHcHdHcHdHaHae'HONHbÕHbÕHcÕHdÕHcÕHdÕHaÕHaÕHOH2OACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hCH3HHfÕ!!,,#&$*&!03*0>AKHCJ?*JQ*OANKJOC?>*YCHL*B>HLA?JP **"!"#$%&'?) (?)'@9&'%&367".0'.8': 3%6.:"0&'X7.>W'/"79',&7930 .4'37'6.0:7307'6$ %%&07 '.8'*)*',ZF6, !';"&4=&='O*`' "G,&79;4:3%6.:"0&'/"79'OP`'6.0S&%:".0 'X<.77.,W) '!!H3CH2NOHOACC cathode /Ru on ACC anode divided cell by nafion ¨117 Phosphate Buffer/ CH3OH (4:1) pH 7.5, 60 ¡C, 10 hHHH3CNOHOHHH3CHaba'b'cÕ!!,-#&$*&!03*0>AKHCJ?*JQ*OANKJOC?>*YCHL*>HLA?JP ***!"#$%&'?) (H)'@9&'%&367".0'.8':3%6.:"0&'X7.>W'/"79'&7930.4 '37'6.0:7307'6$%%&07'.8' *)* ',ZF6, !';"&4=& ='OO`' "G&79;4:3%6.:"0&'/"79'PM`'6.0S&%:".0'X<.77.,W)' "'H3CH2NOHOACC cathode /Ru on ACC anode divided cell by nafion ¨117 Phosphate Buffer/ CH3CH2OH (4:1) pH 7.5, 60 ¡C, 10 hHHH3CNHOHOHHaba'b'H3CHHbÕÕ cÕcÕÕ eÕ!!-.#&$*&!03*0>AKHCJ?*JQ*ABBJ?CFB*AK>HAH>*6E>?>NAH>O*ABBJ?CA*C?*OCHF7*YCHL*>HLA?JP ***!"#$%&'?) (M)'@9&'%&367".0'.8'3,,.0"3'36&737&'X3,,.0 "3W'X7.>W'/"79'&7930.4' 37' 6.0:7307'6$%%& 07'.8'*) *',ZF6, !';"&4=&='TV`'C G7%"&79;43,"0&'/"79'T*`'6.0S&%:".0'X<.77.,W) '!!ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hHNCH3H3CCH3HHbÕHHHHNH4OAc (aq) !!-%#&$*&!03*0>AKHCJ?*JQ*>HL=PABC?>*YCHL*>HLA?JP **"!"#$%&'?) (O)'@9&'%&367".0'.8'&79;43,"0&'X7.>W'/"79'&7930.4'37'6. 0:7307'6$%%&07'.8'*)* ',ZF6, !';"&4=&='T *`' 7%"&79; 43,"0&'30='TP`'6.0S&%:".0'X<.77.,W)' '!!ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hHNCH3H3CCH3HHaÕbÕHHHHH3NCH3HHab!!-&#&$*&!03*0>AKHCJ?*JQ*IC>HL=PABC?>*YCHL*>HLA?JP **"!"#$%&'?) (P)'@9&'%&367".0'.8'="&79;43,"0&'X7.>W'/"79'&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6 ,!';"&4=&='T*`' 7%"& 79; 43,"0&'30='(VV `'6.0S&%:".0 'X<.77.,W)' !'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hHNCH3H3CCH3HHaÕbÕHHHHNH2CH3H3CHHabHH!!-'#&$*&!03*0>AKHCJ?*JQ*ABBJ?CFB*L=INJaCI>*YCHL*COJDNJD=P*APKJLJP ***!"#$%&'?) (Q)'@9&'&0='%&367".0'.8'3,,.0"$,'9;=%.A"=&'X7.>W'/"79'":.>%.>;4'346.9.4';"&4=&='(M`' ="":.>%.> ;43,"0&'37'OV'^+' X<. 77.,W)' !'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ (CH3)2CHOH (19:1) pH 8.5, 60 ¡C, 10 hNH2CH3H3CHCH3aÕbÕHH3CNH4OH(aq) !!-(#&$*&!03*0>AKHCJ?*JQ *ABBJ?CFB*AK>HAH>*YCHL*COJDNJD=P*APKJLJP* **"!"#$%&'?) (T)'@9&'&0='%&367".0'.8'3,,.0"$,'9;=%.A"=&'X7.>W'/"79'":.>%.>;4'346.9.4';"&4=&='OV'`' ="":.>%.>;43,"0&'37'OV'^+'/"79'7%36&'.8'" :.>%.>;43,"0&'X< .77 .,W )!'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ (CH3)2CHOH (19:1) pH 8.5, 60 ¡C, 10 hNH2CH3H3CHCH3aÕbÕHH3CNH4OAc (aq) !!-)#&$*&!03* 0>AKHCJ?*JQ*ICC OJDNJD=PABC?>*YCHL*B>HLA?JP **"!"#$%&'?) *V)'@9&'%&367".0'.8'="":.>%.>;43,"0&'X7.>W'/"79',&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='?V`' "G,&79;4="":.>%.>;43,"0&'30='?H`'6.0S &%:".0'X<.77.,W )''!!ACC cathode /Ru on ACC anode undivided cell by Phosphate Buffer/ CH3OH (19:1) pH 8.5, 60 ¡C, 10 hHNCH3H3CHCH3aÕbÕHH3CNH2CH3H3CHCH3abHH3CCH3cÕ!!-*#&$*&!03*0>AKHCJ?*JQ*ICCOJDNJ D=PABC?>*YCHL*>HLA?JP **"!"#$%&'?) *()'@9&'%&367".0'.8'="":.>%.>;43,"0&'X7.>W'/"79'&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !%;"&4=&=' ?H`' "G&79;4="":.>%.>;43,"0&]'3)5)3)'\s0"#c:'<3:& '30='*H`'6.0S& %:" .0'X<.77.,W)' !'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hHNCH3H3CHCH3aÕbÕHH3CNH2CH3H3CHCH3abHH3CcÕCH3HHdÕ!!-+#&$*&!03*0>AKHCJ? *JQ*GFH=PABC?>*YCHL*>HLA?JP **"!"#$%&'?) **)'@9&'%&367".0'.8' )G<$7;43,"0&'X7.>W/"79'&7930.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='TV`' "1" G="&79;4<$7;43,"0&'30='(VV`'6.0S&%:".0'X <.77.,W)' !'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3CH2OH (19:1) pH 8.5, 60 ¡C, 10 hH3NHHcbCH3HHHHdaNHHHcbCH3HHHHdaH3CHHef!!-,#&$*&!03*0>AKHCJ?*J Q*IC>HL=PABC?>*YCHL *GFHA?JP **"!"#$%&'?) *?)'@9&'%&367".0'.8'="&79;43,"0&'X7.>W'/"79'<$730.4'37'6.0:7307'6$%%&07'.8'*)*',ZF6, !';"&4=&='TV`' "1" G="&79;4<$7343,"0&'30='(VV`'6.0S&%:".0'X<.77.,W)' !'ACC cathode /Ru on ACC anode undivided cell Phosphate Buffer/ CH3(CH 2)3OH (19:1) pH 8.5, 60 ¡C, 10 hNH2CH3HHbaH3CHHHNCH3HHbÕaÕH3CHHH3CHHHHHHcÕdÕfÕH2OeÕ!!--#&$&!03*0>AKHCJ?*JQ *D=NNJPCIC?>*YCHL *fXB>HL=PK=KPJL>aA?J ?>*6ICMCI>I*K>PP7 **"!"#$%&'?) *H)'@9&'%&367".0'.8' >;%%.4"="0& 'X7.>W'/"79' HG,&79;46;64.9&A30.0& '37'6.0:7307'6$%%&07'.8'*)*' ,ZF6, !%8.%,"0#'(n('%37".'.8'6":F7%30: GHG,&79;46;64.9&A;4>; %%.4"="0&'X <.7 7.,W) %'NHAnodeÑRu/ACC /CathodeÑACC divided cell Phosphate Buffer/ Ketone pH 8.5, 60 ¡C, 24 hCH3HHOKetone = NHHbHbHcHdHcHdHaHae'HNHb'Hb'Hc'Hd'Hc'Hd'Ha'Ha'HH2OCH3HHeÕÕ fÕfÕÕ !!%..#&$*&!03*0>AKHCJ?*JQ*D=NNJPC IC?>*YCHL* *!$ XfXB>HL= PK=KPJL>aA?JP*6ICMCI>I*K>PP7 **"!"#$%&'?) *M)''@9&'%&367".0'.8' >;%%.4"="0& 'X7.>W'/"79' ,-$GHG,&79;46;64.9&A30.4 '37'6.0:7307'6$%%&07'.8'*)*' ,ZF6, !%8.%,"0#'*n('%37 ".'.8'6":F 7%3 0:GHG,&79;46;6 4.9&A;4>;%%.4"="0&'X< .77.,W) "'NHNHCH3NHAnodeÑACC /CathodeÑRu/ACC undivided cell Phosphate Buffer/ alcoholpH 8.5, 60 ¡C, 24 hHCH3HHHOHH2OAlcohol = !!%.%#&$*&!03*0>AKHCJ?*JQ*D=NNJPCIC?>*YCHL*f XB>HL=PK=KPJL>aA?J?>*6F?ICMCI>I*K>PP7 ***!"#$%&'?) *O)'@9&'%&367".0'.8' >;%%.4"="0& 'X7.>W'/"79' HG,&79;46;64.9&A30.0& '37'6.0:7307'6$%%&0 7'.8'*)*' ,ZF 6,!%8.%,"0#'*n ('%37".'.8'6":F7%30: GHG,&79;46;64.9&A;4>;%%.4"="0&'X<.77.,W) "'NHNHCH3NHAnodeÑRu/ACC /CathodeÑACC undivided cell Phosphate Buffer/ Ketone pH 8.5, 60 ¡C, 24 hHCH3HHHOH2OKetone = !!%.#X!(*JQ*HL>*0>AKHCJ?*JQ*D=NNJPCIC?>*YCHL 2*!$ XfXB>HL=PK=KPJL>aA?JP* **""!"#$%&'?) *P)'f+GJR'.8' ,-$'X',>'D'(?P G(?P)M' %W'30='+./)$GHG,&79;46;64 .9&A;4>;%%.4"="0&'X(TV G(T*'%W)',55"'274;-;<39=?@2?2@5=3>?@ ;&;F?005@7G7:3 !901:4 ;-;<39=?@2?2@ 5=3>?@ ;&;F?005@7G7:3 !274;-;<39=?@2?2@5=3>1:5@ !H5@I 3:9!CG739=?@!39=30E !3/0!3/0"!NHNHCH3NH38%62%HOACC anode /Ru on ACC cathode undivided cell Phosphate Buffer/ ROH (19:1) pH 8.5, 60 ¡C, 24 hHCH3ROH =HHH16%!!%.'#.NAEB>?HAHCJ?O*JQ*f XB>HL=PK=KPJL>a=PD=NNJPCIC?>*6I>IFK>I*QNJB*OD>KHNA7 **"""!"#$%&'?) *Q)'K%.>.:&=',3::':>&67%.,&7%;'8%3#,&0737".0'.8'H G,&79;46;64.9& A;4>;%%.4"="0& '''N=167 H- CH 3N152MN!-cleavage N1,5-H abstraction !-cleavage N=110 M!!%.(#!"#$%&'( ?*( '&8-!%,01(02(!#'40@6+,! 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