不对称羟胺化反应

1、1会计学不对称羟胺化反应不对称羟胺化反应 Hisashi Yamamoto was born in Kobe, Japan, in 1963. He received his Bachelor s degree from Kyoto University in 1967, where he got his start in a research group headed by Prof. H. Nozaki. Professor Yamamoto received his Ph.D. from Harvard University under mentorship of Corey. Yama

2、moto has become aware of the importance of chiral Lewis acids in asymmetric synthesis. In 1985, he first introduced binaphthol as a ligand for chiral Lewis acid catalysts. This work was the forerunner of a vast amount of present-day research on the binaththol based chiral Lewis acid catalyst. More r

3、ecently, silver catalyzed ene and aldol reactions were reported which are remarkably effective in a series of asymmetric transformations. To date, Professor Yamamoto has co-authored over 400 publications and 100 reviews.Hisashi Yamamoto第2页/共21页第3页/共21页第4页/共21页Angew. Chem .Int. Ed 2002, 41, 2986Yamam

4、otos workYield:37-94%TMSOR1R3R2NOOR1R1R2ONHPh0,1hEt3SiOTf (5 mmol%)第5页/共21页XR1R3R2NOOR1R1R2ONHPh(R)-BINAP-78,2hTHFAgOTfOSnR395% yield, 97%eeOSnR396% yield, 95%ee94% yield, 87%ee92% yield, 90%ee96% yield, 85%ee93% yield, 92%ee95% yield, 82%ee92% yield, 94%eePhOSnR3R3SnOOSnR3R3SnOOSnR3OSnR3Yamamotos w

5、orkJ. Am . Chem. Soc 2003,125, 6038第6页/共21页NONR1RRR1OOHOHcat=30 mol% cat-88-78,12h( )nRR( )nOONHPhyield: 69-89%; ee: 70-93%Yamamotos workJ. Am . Chem. Soc 2005,127,1080第7页/共21页Angew. Chem .Int. Ed 2003, 42, 4247Zhong guofu and Macmillans workL-proline(20 mol%) DMSO,RT20min,then NaBH4,EtOHNOROROHONHP

6、hyield: 54-86%; ee: 94-99%.J. Am . Chem. Soc 2003,125,10808第8页/共21页Hayashi and Cordovas workAngew. Chem. Int. Ed 2004,43,1109Angew. Chem. Int. Ed 2004,43,1112yield: 64-91%; ee99%yield: 44-96%; ee99%R1OR2NOL-prolineR1OR2ONHPh第9页/共21页NHCOOHTBSOOR1R2NO10% 1OR1R2ONHPh1DMFy yi i e el l d d: : 4 45 5- -7

7、78 8% % ; ; e ee e: :9 98 8- -9 99 9% %Adv. synth. catal 2004,346,1435第10页/共21页NHOR1R2NO20%CATOR1R2ONHPhDMSO,RTNHSOOCF3subsubyieldeeOOOOOOO8499869471999897Tetrahedron letter 45(2004)7235第11页/共21页NHONHOR1NO10%CATDMSO,RTSOOMeROR1RONHPhsubyieldeeOOHOOO809974669899O5499第12页/共21页NHNHNNNTetrahedron letter

8、 47(2006),9067第13页/共21页NOCAT(20 mol%) DMSO,RT20min,then NaBH4,EtOHR1OR2R1OR2ONHPh NHNHNNNyieldeesubOOOOOOO948775676569999999989898Yamamotos workPans 2005, 101, 5374.第14页/共21页J. Am . Chem. Soc 2006,128,6046Maruokas work手性手性Lewis碱催化的醛酮碱催化的醛酮-羟胺化反应羟胺化反应yield:70-90%; ee: 97-99%NHCPh2OHCPh2OHNORO10 mol%c

9、at , NaBH4,EtOHROHNOHPh cat =第15页/共21页J. AM . CHEM. SOC 126(2004),5360OSnBu395% yield, 99%eeOSnBu394% yield, 77%eeOSnBu397% yield, 98%ee90% yield, 86%ee96% yield, 97%eePhBu3SnOOSnBu3R1Bu3SnOR3R2NO(R)-BINAPEtOCH2CH2OEt-78,2hR1ONPhR2R3OH(AgOTf)2第16页/共21页RHONO10%CATPhCH3,2-3dRHONPhHONaBH4OOHOsubyieldee

10、(%)(%)HOHOButHOPrtHO74595346554669597133Chem.Commun 2006, 429NHNHOOHPhPh第17页/共21页Mechanism:Org. Lett. 2002, 4, 3579第18页/共21页第19页/共21页第20页/共21页第21页/共21页NHCOOHTBSOOR1R2NO10% 1OR1R2ONHPh1DMFy yi i e el l d d: : 4 45 5- -7 78 8% % ; ; e ee e: :9 98 8- -9 99 9% %Adv. synth. catal 2004,346,1435第10页/共21页NHOR1R2NO20%CATOR1R2ONHPhDMSO,RTNHSOOCF3subsubyieldeeOOOOOOO8499869471999897Tetrahedron letter 45(2004)7235第11页/共21页NHONHOR1NO10%CATDMSO,RTSOOMeROR1RONHPhsubyieldeeOOHOOO809974669899O5499第12页/共21页RHON