A general organocatalyst for direct α-functionalization of aldehydes:: Stereoselective C-C, C-N, C-F, C-BR, and C-S bond-forming reactions.: Scope and mechanistic insights

被引：554

作者：

Franzén, J ^{[1
]}

Marigo, M ^{[1
]}

Fielenbach, D ^{[1
]}

Wabnitz, TC ^{[1
]}

Kjaersgaard, A ^{[1
]}

Jorgensen, KA ^{[1
]}

机构：

[1] Aarhus Univ, Dept Chem, Danish Natl Res Fdn, Ctr Catalysis, DK-8000 Aarhus C, Denmark

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 51期

关键词：

D O I：

10.1021/ja056120u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts.

引用

页码：18296 / 18304

页数：9

共 90 条

[21] Chowdari NS, 2003, SYNLETT, P1906
[22] 5-pyrrolidin-2-yltetrazole: A new, catalytic, more soluble alternative to proline in an organocatalytic asymmetric Mannich-type reaction
Cobb, AJA
Shaw, DM
Ley, SV
[J]. SYNLETT, 2004, (03) : 558 - 560
[23] The direct amino acid-catalyzed asymmetric incorporation of molecular oxygen to organic compounds
Córdova, A
Sundén, H
Engqvist, M
Ibrahem, I
Casas, J
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (29) : 8914 - 8915
[24] The direct catalytic asymmetric α-aminooxylation reaction:: Development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations
Córdova, A
Sundén, H
Bogevig, A
Johansson, M
Himo, F
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (15) : 3673 - 3684
[25] The direct catalytic asymmetric Mannich reaction
Córdova, A
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (02) : 102 - 112
[26] anti-selective SMP-catalyzed direct asymmetric Mannich-type reactions:: synthesis of functionalized amino acid derivatives
Córdova, A
Barbas, CF
[J]. TETRAHEDRON LETTERS, 2002, 43 (43) : 7749 - 7752
[27] Proline-catalyzed one-step asymmetric synthesis of 5-hydroxy-(2E)-hexenal from acetaldehyde
Córdova, A
Notz, W
Barbas, CF
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (01) : 301 - 303
[28] A highly enantioselective route to either enantiomer of both α- and β-amino acid derivatives
Córdova, A
Watanabe, S
Tanaka, F
Notz, W
Barbas, CF
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (09) : 1866 - 1867
[29] A highly enantioselective amino acid-catalyzed route to functionalized α-amino acids
Córdova, A
Notz, W
Zhong, GF
Betancort, JM
Barbas, CF
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (09) : 1842 - 1843
[30] In the golden age of organocatalysis
Dalko, PI
Moisan, L
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (39) : 5138 - 5175

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