1、Seminar Seminar II II報(bào)報(bào) 告告 內(nèi)內(nèi) 容容引言引言有機(jī)催化的動態(tài)動力學(xué)拆分反應(yīng)有機(jī)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(xiàn)參考文獻(xiàn)引引 言言SRPRSSPSfastkAslowkBP1RP1SP2RP2SSR + Z1SS + Z1SR + Z2SS + Z2k1(R)k1(S)k2(R)k2(S)kBSRPRSSPSfastkAslowkinvkinv-1racemisation有機(jī)小分有機(jī)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(jià)格便宜價(jià)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