Enantioselective Synthesis of Chiral Allenoates by Guanidine-Catalyzed Isomerization of 3-Alkynoates

被引：220

作者：

Liu, Hongjun ^{[1
]}

Leow, Dasheng ^{[1
]}

Huang, Kuo-Wei ^{[1
]}

Tan, Choon-Hong ^{[1
]}

机构：

[1] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 21期

关键词：

ASYMMETRIC-SYNTHESIS; BICYCLIC GUANIDINE; 11-DEOXYANTHRACYCLINE SYNTHESIS; REGIOSPECIFIC SYNTHESIS; ALLENES; CYCLIZATION; PALLADIUM; BASE; 6-ALKOXY-2-PYRONES; HYDROSILYLATION;

D O I：

10.1021/ja901528b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report that chiral bicyclic guanidine 1 is found to catalyze the isomerization of alkynes to chiral allenes with high enantioselectivities. This Bronsted base catalyzed 1,3-proton shift reaction, an efficient and atom economical reaction, proceeds through deprotonation and protonation sequences. The axial chirality of the allenes is efficiently transferred to functionalized butenolides and cycloaddition products. We also successfully demonstrate the stereospecific synthesis of butenolide through allenoate cyclization with a catalytic cationic Au(I) complex.

引用

页码：7212 / +

页数：3

共 45 条

[1]

Brewster J.H., 1967, Top. Stereochem, V2, P1, DOI 10.1002/9780470147115.ch1

[2] 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

[3] CHIRAL INDUCTION IN THE SYNTHESIS OF 4,4-DIMETHYL-1-PHENYLPENTA-1,2-DIENE (1-PH-3-T-BU-ALLENE) CATALYZED BY CHIRAL PHOSPHINE COMPLEXES OF PALLADIUM [J].

DEGRAAF, W ;

BOERSMA, J ;

VANKOTEN, G ;

ELSEVIER, CJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 378 (01) :115-124

[4] SYNTHESIS OF 5-ALKYL-4-BROMO-5-HYDROXY-2(5H)-FURANONES AND 5-ALKYLIDENE-4-BROMO-2(5H)-FURANONES [J].

FONT, J ;

GRACIA, A ;

DEMARCH, P .

TETRAHEDRON LETTERS, 1990, 31 (38) :5517-5520

[5] Palladium-catalyzed asymmetric hydrosilylation of 4-substituted 1-buten-3-ynes. Catalytic asymmetric synthesis of axially chiral allenylsilanes [J].

Han, JW ;

Tokunaga, N ;

Hayashi, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (51) :12915-12916

[6]

Hashmi ASK, 2000, ANGEW CHEM INT EDIT, V39, P2285, DOI 10.1002/1521-3773(20000703)39:13<2285::AID-ANIE2285>3.0.CO

[7]

2-F

[8] Gold catalysis: Evidence for the in-situ reduction of gold(III) during the cyclization of allenyl carbinols [J].

Hashmi, ASK ;

Blanco, MC ;

Fischer, D ;

Bats, JW .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (06) :1387-1389

[9] Rhodium-catalyzed asymmetric 1,6-addition of aryltitanates to enynones giving axially chiral allenes [J].

Hayashi, T ;

Tokunaga, N ;

Inoue, K .

ORGANIC LETTERS, 2004, 6 (02) :305-307

[10] Synthesis and properties of allenic natural products and pharmaceuticals [J].

Hoffmann-Röder, A ;

Krause, N .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (10) :1196-1216

← 1 2 3 4 5 →