Cooperative dual catalysis: Application to the highly enantioselective conjugate cyanation of unsaturated imides

被引：306

作者：

Sammis, GM ^{[1
]}

Danjo, H ^{[1
]}

Jacobsen, EN ^{[1
]}

机构：

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 32期

关键词：

D O I：

10.1021/ja046653n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to α,β-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex. Copyright © 2004 American Chemical Society.

引用

页码：9928 / 9929

页数：2

共 22 条

[1] On the mechanism of asymmetric nucleophilic ring-opening of epoxides catalyzed by (salen)Cr-III complexes [J].

Hansen, KB ;

Leighton, JL ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (44) :10924-10925

[2] Mechanism of enantioselective Ti-catalyzed strecker reaction: Peptide-based metal complexes as bifunctional catalysts [J].

Josephsohn, NS ;

Kuntz, KW ;

Snapper, ML ;

Hoveyda, AH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (47) :11594-11599

[3] Asymmetric hydrocyanation of hydrazones catalyzed by lanthanide-PYBOX complexes [J].

Keith, JM ;

Jacobsen, EN .

ORGANIC LETTERS, 2004, 6 (02) :153-155

[4] Catalytic enantioselective meso-epoxide ring opening reaction with phenolic oxygen nucleophile promoted by gallium heterobimetallic multifunctional complexes [J].

Matsunaga, S ;

Das, J ;

Roels, J ;

Vogl, EM ;

Yamamoto, N ;

Iida, T ;

Yamaguchi, K ;

Shibasaki, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (10) :2252-2260

[5] Mechanistic studies of the zirconium-triisopropanolamine-catalyzed enantioselective addition of azide to cyclohexene oxide [J].

McCleland, BW ;

Nugent, WA ;

Finn, MG .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (19) :6656-6666

[6] Catalytic enantioselective synthesis of quaternary stereocenters via intermolecular C-acylation of silyl ketene acetals: Dual activation of the electrophile and the nucleophile [J].

Mermerian, AH ;

Fu, GC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (14) :4050-4051

[7] Asymmetric synthesis of β-amino acid derivatives via catalytic conjugate addition of hydrazoic acid to unsaturated imides [J].

Myers, JK ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (38) :8959-8960

[8] Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides [J].

Nielsen, LPC ;

Stevenson, CP ;

Blackmond, DG ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (05) :1360-1362

[9] Design of new chiral phase-transfer catalysts with dual functions for highly enantioselective epoxidation of α,β-unsaturated ketones [J].

Ooi, T ;

Ohara, D ;

Tamura, M ;

Maruoka, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (22) :6844-6845

[10] Highly active oligomeric (salen)Co catalysts for asymmetric epoxide ring-opening reactions [J].

Ready, JM ;

Jacobsen, EN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (11) :2687-2688

← 1 2 3 →