Reversal of enantioselectivity by catalyst protonation: Asymmetric hydrocyanation of imines with oxazaborolidines

被引：33

作者：

Berkessel, A ^{[1
]}

Mukherjee, S ^{[1
]}

Lex, J ^{[1
]}

机构：

[1] Univ Cologne, Inst Organ Chem, D-50939 Cologne, Germany

来源：

SYNLETT | 2006年 / 01期

关键词：

oxazaborolidine; asymmetric catalysis; hydrocyanation; imine; protonation;

D O I：

10.1055/s-2005-922757

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new application of chiral oxazaborolidines in asymmetric transformation, namely the hydrocyanation of imines, is described. The effect of protonation of these catalysts on the reactivity and enantioselectivity of hydrocyanations is studied. Significant increase in reaction rate is observed upon protonation of the catalysts, along with the reversal of the sense of stereoinduction.

引用

页码：41 / 44

页数：4

共 32 条

[1] Tuning the enantioselective N-acetylation of racemic amines: A spectacular salt effect [J].

Arseniyadis, S ;

Subhash, PV ;

Valleix, A ;

Mathew, SP ;

Blackmond, DG ;

Wagner, A ;

Mioskowski, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (17) :6138-6139

[2]

Berkessel A, 2005, ASYMMETRIC ORGANOCATALYSIS: FROM BIOMIMETIC CONCEPTS TO APPLICATIONS IN ASYMMETRIC SYNTHESIS, P1, DOI 10.1002/3527604677

[3] Reversal of enantioselectivity in the hydroformylation of styrene with [2S,4S-BDPP]Pt(SnCl3)Cl at high temperature arises from a change in the enantioselective-determining step [J].

Casey, CP ;

Martins, SC ;

Fagan, MA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (17) :5585-5592

[4]

Corey EJ, 1998, ANGEW CHEM INT EDIT, V37, P1987, DOI 10.1002/(SICI)1521-3773(19980817)37:15<1986::AID-ANIE1986>3.0.CO

[5]

2-Z

[6] Enantioselective synthesis of α-amino nitriles from N-benzhydryl imines and HCN with a chiral bicyclic guanidine as catalyst [J].

Corey, EJ ;

Grogan, MJ .

ORGANIC LETTERS, 1999, 1 (01) :157-160

[7] Asymmetric Diels-Alder reactions catalyzed by a triflic acid activated chiral oxazaborolidine [J].

Corey, EJ ;

Shibata, T ;

Lee, TW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (15) :3808-3809

[8] Catalytic enantioselective Strecker reactions and analogous syntheses [J].

Gröger, H .

CHEMICAL REVIEWS, 2003, 103 (08) :2795-2827

[9] Syntheses of optically active α-amino nitriles by asymmetric transformation of the second kind using a principle of O.!Dimroth [J].

Hassan, NA ;

Bayer, E ;

Jochims, JC .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1998, (22) :3747-3757

[10] ASYMMETRIC REDUCTION OF AROMATIC KETONES WITH CHIRAL ALKOXY-AMINE-BORANE COMPLEXES [J].

HIRAO, A ;

ITSUNO, S ;

NAKAHAMA, S ;

YAMAZAKI, N .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (07) :315-317

← 1 2 3 4 →