有機催化的動態(tài)動力學(xué)拆分

1、Seminar Seminar II II報報 告告 內(nèi)內(nèi) 容容引言引言有機催化的動態(tài)動力學(xué)拆分反應(yīng)有機催化的動態(tài)動力學(xué)拆分反應(yīng)小結(jié)小結(jié)參考文獻參考文獻引引 言言SRPRSSPSfastkAslowkBP1RP1SP2RP2SSR + Z1SS + Z1SR + Z2SS + Z2k1(R)k1(S)k2(R)k2(S)kBSRPRSSPSfastkAslowkinvkinv-1racemisation有機小分有機小分子催化劑子催化劑的優(yōu)勢的優(yōu)勢催化劑來源催化劑來源廣泛廣泛易制備易制備價格便宜價格便宜易操作易操作低毒性低毒性動態(tài)動力學(xué)拆分反應(yīng)動態(tài)動力學(xué)拆分反應(yīng)NOOOROClH2COONHRC

2、lH2CO(DHQD)2AQN Et2O, 20oCOHOONNNNMeOOMeOOEtEt(DHQD)2AQNHH75-87% yield, 59-75% eePNOOORHPNOOORHPNOO-OROORNHPRHNR3krac*HNR3+*+NR3krac*OORNHPRHNR3*ROHslowNR3*ROHfastkskfS-2R-2S-1R-1R = AlkylOOOOROOROHR(DHQD)2AQN (10 mol%)OONNNNMeOOMeOOEtEt(DHQD)2AQNHH65-80% yield, 60-96% eeROH, Et2O, 20oCNORPhOOcataly

3、st, toluene, 20oCOHORNHOPhNHSNHt-BuONBnNMe2catalyst28-98% yield, 78-95% eeOOR3NHOR1R2HOOR3NHOR1HR2NOR1OHR2NOR1OR2HNOR1OHR2R3OHcatalystR3OHcatalystAent-ABent-BNORR1catalyst, toluene, 20oCO93-98% yield, 49-78% eeRHNOR2OR1OR2OHNMe2NFecatalystSOSOHCOOSOOOHSOL-prolinewet DMSO+56% yield, 98% eeSOSOHCOOSOO

4、OHSO+NHNHNNNSOOOHSOHSOOOHSOSiEt3wet DMSO75% (98% ee)LisBu3BH, THF83%Et3SiOTf, 2,6-lutidine, CH2Cl2, 0 oC97%SOOOHSOSiEt3SOOXSOSiEt3SOOSOSiEt3OOOSiEt3OHONaH,CS2, MeI93%X=OCS2MeBu3SnH, AIBN, PhMe 110oCRaney-Ni, EtOH,HOAc, CH2Cl2,91%82%SerricorninONR2RONi-Pr2CHORONi-Pr2OHOONR2CHOOHOL-ProlineacetoneL-Pro

5、lineacetone87-89% yield, 91-92% ee79-100% yield, 83-95% eeCO2R2OR1R2O2CR2O2COOHR2O2CHR1L-prolineacetoneMeCN44-85% yield, 44-83% de, 87-99% ee 40-96% yield, 80-98% ee+NHOMeOt-BuOOHH+OOP OHArAr5 mol% cat.5A MS, 72h benzeneH2NR3CHOR1R2NHR3R2R1Ocat.Ar = 2,4,6-(i-Pr)3C6H2 NHR5OOCHHH2NR3R1R2NHR3R2R1R2R1NH

6、R3COOR4NR5OOCCOOR4OHR2R1HNHR3R2R1NHR3R2R1NHHR3HX*-H2OracemizationX*-+ OAcONuONO2NO2* 80% yield, 56% ee(R)-Cl-MeO-BIPHEPNuH/THFNu =NHOO EWGR1NuR2EWGR1AcOR2EWGR1R2PR3EWGR1R2PR3NuH = 4,5-Dichlorophthalimide (200 mol%)PR3Electrophile-Leaving GroupIon-PairElectrophile-NucleophileIon-PairOAc+ Nu-HHOAc + N

7、u:OAcNu:(20 mol%) SRCO2EtNO2SHCO2EtRNO2XX+toluene, RTcatalyst (10 mol%)HNNNHSArHMeOAr= 3,5,-(CF3)2C6H3catalyst42-98% yield, 92-99%ee SRCO2EtNO2SHCO2EtRNO2XX+SRCO2EtNO2XHMichael reactionDKRstep 1step 2highly acidic SR3R1R2SR3R2R1PR3R1R2PR3R2R1 SOClSOORONHBnOHNi-PrONHOHNi-PrOOMeOt-BuHNOi-PrNHOHNOHNOt-BuOOt-BuNNNN Trtcatalyst/THF-78oC+ ROHcatalyst61-99% yield, 80-99% ee AcONSClOSOt-BuMeOHOt-BuOHcatalyst/CH2Cl2-78oC+RRNHcatalyst68-93% yield, 88-93% ee