Regiodivergent epoxide opening:: A concept in stereoselective catalysis beyond classical kinetic resolutions and desymmetrizations

被引：67

作者：

Gansaeuer, Andreas ^{[1
]}

Fan, Chun-An ^{[1
]}

Keller, Florian ^{[1
]}

Karbaum, Peter ^{[1
]}

机构：

[1] Univ Bonn, Kekule Inst Org Chem & Biochem, D-53127 Bonn, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2007年 / 13卷 / 29期

关键词：

catalysis; enantioselectivity; epoxides; radical reactions; regioselectivity;

D O I：

10.1002/chem.200701021

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An approach to highly regiodivergent epoxide openings (REOs) is presented. The very popular kinetic resolutions of epoxides and openings of weso-epoxides constitute subclasses of such REOs. REOs are attractive for parallel resolutions, double asymmetric reactions of enantiomerically enriched epoxides, and for semisynthetic applications in the functionalization of natural products. They have been notoriously difficult to realize by means of SN2 mechanisms. Our titanocene-catalyzed radical REO addresses this issue by decoupling epoxide opening and radical trapping and is firmly based on a mechanistic study of the reductive epoxide opening. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：8084 / 8090

页数：7

共 76 条

[1]

[Anonymous], 2003, ANGEW CHEM, V115, P5714

[2] The development of scalemic multidentate niobium complexes as catalysts for the highly stereoselective ring opening of meso-epoxides and meso-aziridines [J].

Arai, Kenzo ;

Lucarini, Simone ;

Salter, Matthew M. ;

Ohta, Kentaro ;

Yamashita, Yasuhiro ;

Kobayashi, Shuj .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (26) :8103-8111

[3] Unified synthesis of eudesmanolides, combining biomimetic strategies with homogeneous catalysis and free-radical chemistry [J].

Barrero, AF ;

Rosales, A ;

Cuerva, JM ;

Oltra, JE .

ORGANIC LETTERS, 2003, 5 (11) :1935-1938

[4]

Bertozzi F, 2001, ANGEW CHEM INT EDIT, V40, P930, DOI 10.1002/1521-3773(20010302)40:5<930::AID-ANIE930>3.0.CO

[5]

2-7

[6]

BERTOZZI F, 2001, ANGEW CHEM, V113, P956

[7]

Brandes BD, 2001, SYNLETT, P1013

[8] SYNTHESIS OF NEW LIGANDS FOR TRANSITION-METAL COMPLEXES - MENTHYL-CYCLOPENTADIENES AND NEOMENTHYL-CYCLOPENTADIENES [J].

CESAROTTI, E ;

KAGAN, HB ;

GODDARD, R ;

KRUGER, C .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1978, 162 (03) :297-309

[9]

Cuerva J. M., 2006, TOP CURR CHEM, V264, P63, DOI DOI 10.1007/128_025

[10]

Curran D. P., 1996, STEREOCHEMISTRY RADI

← 1 2 3 4 5 6 7 8 →