Asymmetric Counteranion-Directed Transition-Metal Catalysis: Enantioselective Epoxidation of Alkenes with Manganese(III) Salen Phosphate Complexes

被引：177

作者：

Liao, Saihu ^{[1
]}

List, Benjamin ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, D-5470 Mulheim, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 03期

关键词：

ACDC; alkenes; asymmetric epoxidation; chiral counteranions; phosphates; ACHIRAL (SALEN)MANGANESE(III) COMPLEX; BOND-FORMING REACTIONS; UNFUNCTIONALIZED OLEFINS; CHIRAL ANION; MN-III(SALEN)-CATALYZED EPOXIDATION; ALPHA; BETA-UNSATURATED KETONES; ACID; CYCLOPROPANATION; COUNTERION; CHEMISTRY;

D O I：

10.1002/anie.200905332

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Figure Presented) Figure Presentation Paired up: A highly active and enantioselective ion-pair epoxidation catalyst, consisting of an achiral Mn |||-salen complex and a chiral phosphate counteranion, mediates the epoxidization of a wide range of alkenes with high yields and enantioselectivities (see scheme). The unique role of the counteranion is to stabilize an enantiomorphic conformation of the cationic Mn catalyst. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：628 / 631

页数：4

共 48 条

[1] Asymmetric catalysis of carbon-carbon bond-forming reactions using metal(salen) complexes [J].

Achard, TRJ ;

Clutterbuck, LA ;

North, M .

SYNLETT, 2005, (12) :1828-1847

[2] cis-stilbene and (1α,2β,3α)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the MnIII(salen)-catalyzed epoxidation:: Influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer [J].

Adam, W ;

Roschmann, KJ ;

Saha-Möller, CR ;

Seebach, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) :5068-5073

[3]

Aikawa K., 2009, Angew. Chem, V121, P6189

[4] Axial Chirality Control of Gold(biphep) Complexes by Chiral Anions: Application to Asymmetric Catalysis [J].

Aikawa, Kohsuke ;

Kojima, Masafumi ;

Mikami, Koichi .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (33) :6073-6077

[5] Stronger bronsted acids [J].

Akiyama, Takahiko .

CHEMICAL REVIEWS, 2007, 107 (12) :5744-5758

[6]

[Anonymous], 2006, ANGEW CHEM-GER EDIT

[7] Organocatalytic asymmetric Friedel-Crafts alkylation of indoles with simple α,β-unsaturated ketones [J].

Bartoli, Giuseppe ;

Bosco, Marcella ;

Carlone, Armando ;

Pesciaioli, Fabio ;

Sambri, Letizia ;

Melchiorre, Paolo .

ORGANIC LETTERS, 2007, 9 (07) :1403-1405

[8] Towards phase-transfer catalysts with a chiral anion: inducing asymmetry in the reactions of cations [J].

Carter, C ;

Fletcher, S ;

Nelson, A .

TETRAHEDRON-ASYMMETRY, 2003, 14 (14) :1995-2004

[9] Donor ligand effect on the nature of the oxygenating species in MnIII(salen)-catalyzed epoxidation of olefins:: Experimental evidence for multiple active oxidants [J].

Collman, JP ;

Zeng, L ;

Brauman, JI .

INORGANIC CHEMISTRY, 2004, 43 (08) :2672-2679

[10] Metal-Salen Schiff base complexes in catalysis: practical aspects [J].

Cozzi, PG .

CHEMICAL SOCIETY REVIEWS, 2004, 33 (07) :410-421

← 1 2 3 4 5 →