Mechanism of the Enantioselective Oxidation of Racemic Secondary Alcohols Catalyzed by Chiral Mn(III)-Salen Complexes

被引：51

作者：

Brown, M. Kevin ^{[1
]}

Blewett, Megan M. ^{[1
]}

Colombe, James R. ^{[1
]}

Corey, E. J. ^{[1
]}

机构：

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 32期

基金：

美国国家卫生研究院;

关键词：

HYPERVALENT IODINE(III) REAGENTS; KINETIC RESOLUTION; SALEN COMPLEXES; EPOXIDATION; WATER; HYDROGEN; LIGANDS; ALKENES; FACILE; MODEL;

D O I：

10.1021/ja103103d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The experiments described here clarify the mechanism and origin of the enantioselectivity of the oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)-salen complexes using HOBr, Br-2/H2O/KOAc or PhI(OAc)(2)/H2O/KBr as a stoichiometric oxidant. Key points of the proposed pathway include (1) the formation of a Mn(V) salen dibromide, (2) its subsequent reaction with the alcohol to give an alkoxy-Mn(V) species, and (3) carbonyl-forming elimination to produce the ketone via a highly organized transition state with intramolecular transfer of hydrogen from carbon to an oxygen of the salen ligand.

引用

页码：11165 / 11170

页数：6

共 37 条

[1] Structures of dichloromanganese(IV) complexes with bidentate and tetradentate Schiff base ligands [J].

Asada, H ;

Fujiwara, M ;

Matsushita, T .

POLYHEDRON, 2000, 19 (18-19) :2039-2048

[2] Dual-mode EPR study of Mn(III) salen and the Mn(III) salen-catalyzed epoxidation of cis-β-methylstyrene [J].

Campbell, KA ;

Lashley, MR ;

Wyatt, JK ;

Nantz, MH ;

Britt, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (24) :5710-5719

[3] The Mn(Salen)-catalyzed oxidative kinetic resolution of secondary alcohols: reaction development and scope [J].

Cheng, Qigan ;

Deng, Fanguo ;

Xia, Chungu ;

Sun, Wei .

TETRAHEDRON-ASYMMETRY, 2008, 19 (20) :2359-2362

[4] Enantioselective Catalysis Based on Cationic Oxazaborolidines [J].

Corey, E. J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (12) :2100-2117

[5]

Cotton A. F., 1999, ADV INORG CHEM, V6th

[6] Direct proof for O=Mn-V(salen) complexes [J].

Feichtinger, D ;

Plattner, DA .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (16) :1718-1719

[7] Structural investigation of high-valent manganese-salen complexes by UV/Vis, Raman, XANES, and EXAFS spectroscopy [J].

Feth, MP ;

Bolm, C ;

Hildebrand, JP ;

Köhler, M ;

Beckmann, O ;

Bauer, M ;

Ramamonjisoa, R ;

Bertagnolli, H .

CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (06) :1348-1359

[8] REACTION OF DICHLOROMANGANESE(IV) SCHIFF-BASE COMPLEXES WITH WATER AS A MODEL FOR WATER OXIDATION IN PHOTOSYSTEM-II [J].

FUJIWARA, M ;

MATSUSHITA, T ;

SHONO, T .

POLYHEDRON, 1985, 4 (11) :1895-1900

[9] Highly enantioselective benzylic hydroxylation with concave type of (salen)manganese(III) complex [J].

Hamada, T ;

Irie, R ;

Mihara, J ;

Hamachi, K ;

Katsuki, T .

TETRAHEDRON, 1998, 54 (34) :10017-10028

[10] Oxidative kinetic resolution of 1-phenylethanol catalyzed by sugar-based salen-Mn(III) complexes [J].

Han, Furong ;

Zhao, Jiquan ;

Zhang, Yuecheng ;

Wang, Weiyu ;

Zuo, Yanyan ;

An, Junwei .

CARBOHYDRATE RESEARCH, 2008, 343 (09) :1407-1413

← 1 2 3 4 →