不对称羟胺化反应.pptx

光活性的-羟基醛酮结构单元存在于很多重要的天然产物中，而且是很重要的合成子。醛酮的-羟胺化反应是构建光活性的-羟基醛酮结构单元的一个很新颖的方法。第1页/共21页 Hisashi Yamamoto was born in Kobe,Japan,in 1963.He received his Bachelors 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.Yamamoto 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 recently,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Hisashi Yamamotos outstanding work on nitroso aldol recation1.Momiyama,N.;Yamamoto,H.Angew.Chem.Int.Ed.2002,41,2986.2.Momiyama,N.;Yamamoto,H.J.Am.Chem.Soc.2003,125,6038.3.Momiyama,N.;Yamamoto,H.J.Am.Chem.Soc.2005,127,1080.4.Momiyama,N.;Torii,H.;Saito,S.;Yamamoto,H.Pans 2005,101,5374.5.Yamamoto Y.;Momiyama,N.;Yamamoto,H.J.Am.Chem.Soc.2004,126,5962.6.Momiyama,N.;Yamamoto,H.Org.Lett 2004,126,5962.7.Momiyama,N.;Yamamoto,H.J.Am.Chem.Soc.2004,126,5360.第3页/共21页Armando Cordova:The Arrhenius Laboratory of Stockholm University1.Bgevig,A.;Sundn,H.;Crdova,A.Angew.Chem.Int.Ed.2004,43,1109.2.Crdova,A.;Johansson,M.;Bgevig,A.;Sundn,H.;Chem.Eur.J.2004,10,3673.3.Sundn,H.;Dahin,N.;Ibrabem,I.;Adolfsson,H.;Crdova,A.Teterahedron.Letters.2005,46,3385.第4页/共21页手性手性lewis酸催化的酸催化的a a-胺氧化反应胺氧化反应Angew.Chem.Int.Ed 2002,41,2986Yamamotos workYield:37-94%第5页/共21页Yamamotos workJ.Am.Chem.Soc 2003,125,6038第6页/共21页Yamamotos workJ.Am.Chem.Soc 2005,127,1080第7页/共21页 脯胺酸及其衍生物催化的a-胺氧化反应Angew.Chem.Int.Ed 2003,42,4247Zhong guofu and Macmillans workJ.Am.Chem.Soc 2003,125,10808第8页/共21页Hayashi and Cordovas work第9页/共21页Hayashis work:第10页/共21页第11页/共21页Tetrahedron letters 2005,46,3385.第12页/共21页Tetrahedron letter 47(2006),9067第13页/共21页Yamamotos 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第15页/共21页手性手性Lewis酸催化的醛酮酸催化的醛酮-羟胺化反应羟胺化反应第16页/共21页手性手性Lewis碱催化的醛酮碱催化的醛酮-羟胺化羟胺化第17页/共21页Mechanism:Org.Lett.2002,4,3579第18页/共21页第19页/共21页Summary and Outlook:The catalytic,asymmetric-amination and oxygenation of carbonyl compounds represents a valuable advance in synthetic methodology.A deeper understanding of the mechanism and the factors that govern O versus N selectivity with nitroso compounds will allow for innovation in catalyst design.In addition,more convenient electrophilic sources of nitrogen and oxygen along with broadened and general substrate scope would be a welcome advance.第20页/共21页Thanks!第21页/共21页