不對稱羥胺化反應(yīng)

1、1會計學(xué)不對稱羥胺化反應(yīng)不對稱羥胺化反應(yīng) 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頁/共21頁第3頁/共21頁第4頁/共21頁Angew. Chem .Int. Ed 2002, 41, 2986Yamam

4、otos workYield:37-94%TMSOR1R3R2NOOR1R1R2ONHPh0,1hEt3SiOTf (5 mmol%)第5頁/共21頁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頁/共21頁NONR1RRR1OOHOHcat=30 mol% cat-88-78,12h( )nRR( )nOONHPhyield: 69-89%; ee: 70-93%Yamamotos workJ. Am . Chem. Soc 2005,127,1080第7頁/共21頁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頁/共21頁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頁/共21頁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頁/共21頁NHOR1R2NO20%CATOR1R2ONHPhDMSO,RTNHSOOCF3subsubyieldeeOOOOOOO8499869471999897Tetrahedron letter 45(2004)7235第11頁/共21頁NHONHOR1NO10%CATDMSO,RTSOOMeROR1RONHPhsubyieldeeOOHOOO809974669899O5499第12頁/共21頁NHNHNNNTetrahedron letter

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

9、at , NaBH4,EtOHROHNOHPh cat =第15頁/共21頁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頁/共21頁RHONO10%CATPhCH3,2-3dRHONPhHONaBH4OOHOsubyieldee

10、(%)(%)HOHOButHOPrtHO74595346554669597133Chem.Commun 2006, 429NHNHOOHPhPh第17頁/共21頁Mechanism:Org. Lett. 2002, 4, 3579第18頁/共21頁第19頁/共21頁第20頁/共21頁第21頁/共21頁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頁/共21頁NHOR1R2NO20%CATOR1R2ONHPhDMSO,RTNHSOOCF3subsubyieldeeOOOOOOO8499869471999897Tetrahedron letter 45(2004)7235第11頁/共21頁NHONHOR1NO10%CATDMSO,RTSOOMeROR1RONHPhsubyieldeeOOHOOO809974669899O5499第12頁/共21頁RHON