Metal/linked-BINOL complexes: Applications in direct catalytic asymmetric Mannich-type reactions

被引：92

作者：

Shibasaki, Masakatsu ^{[1
]}

Matsunaga, Shigeki ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2006年 / 691卷 / 10期

基金：

日本学术振兴会;

关键词：

asymmetric catalysis; asymmetric synthesis; bifunctional catalysis; linked-BINOL; Mannich reaction; beta-amino alcohol; zinc; yttrium; Lewis acid; Bronsted base;

D O I：

10.1016/j.jorganchem.2005.10.025

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Development of metal/linked-BINOL complexes and their applications in direct catalytic asymmetric Mannich-type reactions of hydroxyketones are reviewed. A Et2Zn/linked-BINOL complex was effective for diastereo- and enantioselective synthesis of beta-amino alcohols. By choosing the proper protective groups on the imine nitrogen, either anti- or syn-beta-amino alcohol was obtained in excellent enantioselectivity (up to > 99.5% ee) using the same zinc catalysis. Y{N(SiMe3)(2)}(3)/linked-BINOL complex was effective for various hydroxyketones, affording syn-beta-amino alcohols with high enantioselectivity (up to 98% ee). To broaden the nucleophile scope to carboxylic acid derivatives, N-acylpyrrole was utilized as an ester equivalent donor. In(O-iPr)(3)/linked-BINOL complex was effective for generating an In-enolate from N-acylpyrrole in situ, giving Mannich adducts with high enantioselectivity (up to 98% ee). (c) 2005 Elsevier B.V. All rights reserved.

引用

页码：2089 / 2100

页数：12

共 88 条

[31] MULTIMACROCYCLIC COMPOUNDS .4. INTERNAL TRIMERISATION OF TRIPLE BONDS OF LINEAR TRIYNES ON A ZIEGLER CATALYST [J].

HUBERT, AJ .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1967, (20) :1984-&

[32] Amino acid-catalyzed direct enantioselective synthesis of β-amino-α-oxyaldehydes [J].

Ibrahem, I ;

Córdova, A .

TETRAHEDRON LETTERS, 2005, 46 (16) :2839-2843

[33] Direct catalytic enantioselective α-aminomethylation of ketones [J].

Ibrahem, I ;

Casas, J ;

Córdova, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (47) :6528-6531

[34] Efficient catalytic enantioselective Mannich-type reactions using a zirconium-bis(binaphthol)methane complex [J].

Ishitani, H ;

Kitazawa, T ;

Kobayashi, S .

TETRAHEDRON LETTERS, 1999, 40 (11) :2161-2164

[35]

Jacobsen E. N., 2003, COMPREHENSIVE ASY S1

[36]

Juhl K, 2001, ANGEW CHEM INT EDIT, V40, P2995, DOI 10.1002/1521-3773(20010817)40:16<2995::AID-ANIE2995>3.0.CO

[37]

2-M

[38] Stable, storable, and reusable asymmetric catalyst: A novel La-linked-BINOL complex for the catalytic asymmetric Michael reaction [J].

Kim, YS ;

Matsunaga, S ;

Das, J ;

Sekine, A ;

Ohshima, T ;

Shibasaki, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (27) :6506-6507

[39] Sequential Wittig olefination-catalytic asymmetric epoxidation with reuse of waste Ph3P(O):: Application of α,β-unsaturated N-acyl pyrroles as ester surrogates [J].

Kinoshita, T ;

Okada, S ;

Park, SR ;

Matsunaga, S ;

Shibasaki, M .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (38) :4680-4684

[40] A novel dinuclear chiral niobium complex for Lewis acid catalyzed enantioselective reactions: Design of a tridentate ligand and elucidation of the catalyst structure [J].

Kobayashi, S ;

Arai, K ;

Shimizu, H ;

Ihori, Y ;

Ishitani, H ;

Yamashita, Y .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (05) :761-764

← 1 2 3 4 5 6 7 8 9 →