有机催化的动态动力学拆分

1、Seminar Seminar II II报报 告告 内内 容容引言引言有机催化的动态动力学拆分反应有机催化的动态动力学拆分反应小结小结参考文献参考文献引引 言言SRPRSSPSfastkAslowkBP1RP1SP2RP2SSR + Z1SS + Z1SR + Z2SS + Z2k1(R)k1(S)k2(R)k2(S)kBSRPRSSPSfastkAslowkinvkinv-1racemisation有机小分有机小分子催化剂子催化剂的优势的优势催化剂来源催化剂来源广泛广泛易制备易制备价格便宜价格便宜易操作易操作低毒性低毒性动态动力学拆分反应动态动力学拆分反应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