不对称羟胺化反应

光活性的α-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α-羟胺化反应是构建光活性的α-羟基醛酮结构单元的一个很新颖的方法。第1页/共21页HisashiYamamotowasborninKobe,Japan,in1963.HereceivedhisBachelor’sdegreefromKyotoUniversityin1967,wherehegothisstartinaresearchgroupheadedbyProf.H.Nozaki.ProfessorYamamotoreceivedhisPh.D.fromHarvardUniversityundermentorshipofCorey.YamamotohasbecomeawareoftheimportanceofchiralLewisacidsinasymmetricsynthesis.In1985,hefirstintroducedbinaphtholasaligandforchiralLewisacidcatalysts.Thisworkwastheforerunnerofavastamountofpresent-dayresearchonthebinaththolbasedchiralLewisacidcatalyst.Morerecently,silvercatalyzedeneandaldolreactionswerereportedwhichareremarkablyeffectiveinaseriesofasymmetrictransformations.Todate,ProfessorYamamotohasco-authoredover400publicationsand100reviews.HisashiYamamoto第2页/共21页HisashiYamamoto’soutstandingworkonnitrosoaldolrecation

[1].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.Pans2005,101,

5374.[5].YamamotoY.;Momiyama,N.;Yamamoto,H.J.Am.Chem.Soc.2004,126,

5962.[6].Momiyama,N.;Yamamoto,H.Org.Lett2004,126,

5962.[7].Momiyama,N.;Yamamoto,H.

J.Am.Chem.Soc.2004,126,

5360.第3页/共21页ArmandoCordova:TheArrheniusLaboratoryofStockholmUniversity[1].Bøgevig,A.;Sundén,H.;Córdova,A.

Angew.Chem.Int.Ed.2004,43,1109.[2].Córdova,A.;Johansson,M.;Bøgevig,A.;Sundén,H.;Chem.Eur.J.2004,10,3673.[3].Sundén,H.;Dahin,N.;Ibrabem,I.;Adolfsson,H.;Córdova,A.

Teterahedron.Letters.2005,46,3385.第4页/共21页手性lewis酸催化的a-胺氧化反应Angew.Chem.Int.Ed

2002,41,2986Yamamoto’sworkYield:37-94%第5页/共21页Yamamoto’sworkJ.Am.Chem.Soc

2003,125,6038第6页/共21页Yamamoto’sworkJ.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

2003,42,4247ZhongguofuandMacmillan’sworkJ.Am.Chem.Soc

2003,125,10808第8页/共21页HayashiandCordova’swork第9页/共21页Hayashi’swork:第10页/共21页第11页/共21页Tetrahedronletters2005,46,3385.第12页/共21页Tetrahedronletter47(2006),9067第13页/共21页Yamamoto’sworkPans2005,101,

5374.第14页/共21页J.Am.Chem.Soc

2006,128,6046Maruoka’swork手性Lewis碱催化的醛酮α-羟胺化反应第15页/共21页手性Lewis酸催化的醛酮α-羟胺化反应第16页/共21页手性Lewis碱催化的醛酮α-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SummaryandOutlook:Thecatalytic,asymmetricα-aminationandoxygenationofcarbonylcompoundsrepresentsavaluableadvanceinsyntheticmethodology.AdeeperunderstandingofthemechanismandthefactorsthatgovernOversusNselectivitywithnitrosocompoundswillallowforinnovationincatalystdesign.Inaddition,moreconven