Highly enantioselective catalytic asymmetric Claisen rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ethers

被引：48

作者：

Abraham, L ^{[1
]}

Körner, M ^{[1
]}

Hiersemann, M ^{[1
]}

机构：

[1] Tech Univ Dresden, Inst Organ Chem, D-01062 Dresden, Germany

来源：

TETRAHEDRON LETTERS | 2004年 / 45卷 / 18期

关键词：

Claisen rearrangement; asymmetric catalysis; Lewis acid; copper(II)bis(oxazoline);

D O I：

10.1016/j.tetlet.2004.03.047

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Progress in the catalytic asymmetric Claisen rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ether is reported. Application of a more Lewis acidic catalyst, [Cu{(S,S)-t-Bu-box}](H2O)(2)(SbF6)(2), afforded beta-chiral alpha-keto ester with an enantiomeric excess up to 99%. We suggest a highly polarized transition state for the Lewis acid-catalyzed Claisen rearrangement in order to explain the experimental results. (C) 2004 Elsevier Ltd. All rights reserved.

引用

页码：3647 / 3650

页数：4

共 17 条

[1]

Abraham L, 2001, ANGEW CHEM INT EDIT, V40, P4700, DOI 10.1002/1521-3773(20011217)40:24<4700::AID-ANIE4700>3.0.CO

[2]

2-6

[3] Analysis of substituent effects on the claisen rearrangement with ab initio and density functional theory [J].

Aviyente, V ;

Yoo, HY ;

Houk, KN .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (18) :6121-6128

[4] Asymmetric [3.3]-sigmatropic rearrangements in organic synthesis [J].

Enders, D ;

Knopp, M ;

Schiffers, R .

TETRAHEDRON-ASYMMETRY, 1996, 7 (07) :1847-1882

[5] A new copper acetate-bis(oxazoline)-catalyzed, enantioselective Henry reaction [J].

Evans, DA ;

Seidel, D ;

Rueping, M ;

Lam, HW ;

Shaw, JT ;

Downey, CW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (42) :12692-12693

[6] C2-symmetric copper(II) complexes as chiral Lewis acids.: Catalytic enantioselective carbonyl-ene reactions with glyoxylate and pyruvate esters [J].

Evans, DA ;

Tregay, SW ;

Burgey, CS ;

Paras, NA ;

Vojkovsky, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (33) :7936-7943

[7] C2-symmetric chiral bis(oxazoline)-metal complexes in catalytic asymmetric synthesis [J].

Ghosh, AK ;

Packiarajan, M ;

Cappiello, J .

TETRAHEDRON-ASYMMETRY, 1998, 9 (01) :1-45

[8] Synthesis and Lewis acid catalyzed Claisen rearrangement of 2-(1,3-oxazolin-2-yl)-substituted allyl vinyl ethers [J].

Helmboldt, H ;

Hiersemann, M .

TETRAHEDRON, 2003, 59 (23) :4031-4038

[9]

Hiersemann M, 2000, SYNTHESIS-STUTTGART, P1279

[10] Asymmetric claisen rearrangement [J].

Ito, H ;

Taguchi, T .

CHEMICAL SOCIETY REVIEWS, 1999, 28 (01) :43-50

← 1 2 →