Origins of selectivities in proline-catalyzed α-aminoxylations

被引：104

作者：

Cheong, PHY ^{[1
]}

Houk, KN ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 43期

关键词：

D O I：

10.1021/ja0464746

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanisms, transition structures, regioselectivity, and stereoselectivity of proline-catalyzed α-aminoxylation reactions were studied with density functional theory (B3LYP/6-31G(d)). The most favorable transition structure involves the nucleophilic attack of the (E)-proline enamine to the oxygen of the nitrosobenzene with proton transfer from the carboxylic acid to the nitrogen. Enamine attack to the oxygen is favored over the attack on the nitrogen due to the greater basicity of the nitrogen. Previously proposed zwitterionic enaminium pathways are highly disfavored due to the energetic penalty associated with charge separations. Copyright © 2004 American Chemical Society.

引用

页码：13912 / 13913

页数：2

共 29 条

[1] Synthesis of optically active α-hydroxy carbonyl compounds by the catalytic, enantioselective oxidation of silyl enol ethers and ketene acetals with (salen)manganese(III) complexes [J].

Adam, W ;

Fell, RT ;

Stegmann, VR ;

Saha-Möller, CR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (04) :708-714

[2] Synthesis of optically active α-hydroxy ketones by enantioselective oxidation of silyl enol ethers with a fructose-derived dioxirane [J].

Adam, W ;

Fell, RT ;

Saha-Möller, CR ;

Zhao, CG .

TETRAHEDRON-ASYMMETRY, 1998, 9 (03) :397-401

[3] Theory of asymmetric organocatalysis of aldol and related reactions: Rationalizations and predictions [J].

Allemann, C ;

Gordillo, R ;

Clemente, FR ;

Cheong, PHY ;

Houk, KN .

ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (08) :558-569

[4] The nucleophilic addition of nitrones to carbonyl compounds:: insights on the nature of the mechanism of the L-proline induced asymmetric reaction from a DFT analysis [J].

Arnó, M ;

Zaragozá, RJ ;

Domingo, LR .

TETRAHEDRON-ASYMMETRY, 2004, 15 (10) :1541-1549

[5] Origins of opposite absolute stereloselectivities in proline-catalyzed direct Mannich and aldol reactions [J].

Bahmanyar, S ;

Houk, KN .

ORGANIC LETTERS, 2003, 5 (08) :1249-1251

[6] The origin of stereoselectivity in proline-catalyzed intramolecular aldol reactions [J].

Bahmanyar, S ;

Houk, KN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (51) :12911-12912

[7] Direct catalytic enantioselective α-aminoxylation of ketones:: A stereoselective synthesis of α-hydroxy and α,α′-dihydroxy ketones [J].

Bogevig, A ;

Sundén, H ;

Córdova, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (09) :1109-1112

[8] The direct and enantioselective organocatalytic α-oxidation of aldehydes [J].

Brown, SP ;

Brochu, MP ;

Sinz, CJ ;

MacMillan, DWC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) :10808-10809

[9]

CLEMENTE F, UNPUB

[10] The direct catalytic asymmetric α-aminooxylation reaction:: Development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations [J].

Córdova, A ;

Sundén, H ;

Bogevig, A ;

Johansson, M ;

Himo, F .

CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (15) :3673-3684

← 1 2 3 →