Cooperative, highly enantioselective phosphinothiourea catalysis of imine-allene [3+2] cycloadditions

被引：356

作者：

Fang, Yuan-Qing ^{[1
]}

Jacobsen, Eric N. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 17期

关键词：

D O I：

10.1021/ja801344w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new family of phosphinthiourea catalysts was developed for the highly enantioselective synthesis of 2-aryl-2,5-hydropyrroles via a [3 + 2] cycloaddition of an electron-deficient allene with aryl and heteroaryl diphenylphosphinoylimines. The presence of both H(2)O and Et(3)N as additives was found to be important for achieving optimal rates. Dual activation of both nucleophile and electrophile by the bifunctional catalyst is invoked to account for the observed high reactivity and enantioselectivity.

引用

页码：5660 / +

页数：3

共 23 条

[11] Towards perfect catalytic asymmetric synthesis: Dual activation of the electrophile and the nucleophile [J].

Ma, JA ;

Cahard, D .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (35) :4566-4583

[12] Nucleophilic phosphine organocatalysis [J].

Methot, JL ;

Roush, WR .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (9-10) :1035-1050

[13] Asymmetric catalytic aza-Morita-Baylis-Hillman reaction using chiral bifunctional phosphine amides as catalysts [J].

Qi, Ming-Juan ;

Ai, Teng ;

Shi, Min ;

Li, Guigen .

TETRAHEDRON, 2008, 64 (07) :1181-1186

[14] A promising new catalyst family for enantioselective cycloadditions involving allenes and imines:: chiral phosphines with transition metal-CH2-P:: linkages [J].

Scherer, Alexander ;

Gladysz, J. A. .

TETRAHEDRON LETTERS, 2006, 47 (36) :6335-6337

[15]

Segelstein B. E., 2005, U.S. Patent, Patent No. 2005272800

[16] Chiral phosphine lewis bases catalyzed asymmetric aza-Baylis-Hiliman reaction of N-sulfonated imines with activated olefins [J].

Shi, M ;

Chen, LH ;

Li, CQ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (11) :3790-3800

[17] Chiral thiourea-phosphine organocatalysts in the asymmetric Aza-Morita-Baylis-Hillman reaction [J].

Shi, Yong-Ling ;

Shi, Min .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (13) :2129-2135

[18] Schiff base catalysts for the asymmetric Strecker reaction identified and optimized from parallel synthetic libraries [J].

Sigman, MS ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (19) :4901-4902

[19] Highly enantioselective catalytic acyl-Pictet-Spengler reactions [J].

Taylor, MS ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (34) :10558-10559

[20] Synthesis of functionalized cyclopentenes through catalytic asymmetric [3+2] cycloadditions of allenes with enones [J].

Wilson, JE ;

Fu, GC .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (09) :1426-1429

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