The first enantioselective halo aldol reaction of ethyl propiolate and aldehydes

被引：28

作者：

Chen, DJ ^{[1
]}

Timmons, C ^{[1
]}

Liu, JY ^{[1
]}

Headley, A ^{[1
]}

Li, GG ^{[1
]}

机构：

[1] Texas Tech Univ, Dept Biochem & Chem, Lubbock, TX 79409 USA

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 2004卷 / 15期

关键词：

aldol reactions; Morita-Baylis-Hillman esters; chiral salen; enantioselectivity;

D O I：

10.1002/ejoc.200400230

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The first enantioselective halo aldol reaction of ethyl propiolate with aldehydes has been established by using Jacobsen's chiral cyclohexylsalen ligand. The reaction was conducted at -20degreesC in dichloromethane with Et(2)AII as the source of halogen and Lewis acid promoter. Excellent geometric selectivity (only the Z isomer) has been achieved for all 14 examples examined. The reaction works well with aromatic aldehydes; it also works with aliphatic aldehydes and alpha,beta-unsaturated aldehydes, albeit with diminished yields and ee. This method provides the first enantioselective synthesis of beta-iodo Morita-Baylis-Hillman (MBH) esters. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

引用

页码：3330 / 3335

页数：6

共 31 条

[11] TiCl4-n-Bu4NX (X = I, Br, and Cl) combination-induced coupling of α,β-unsaturated ketones with aldehydes [J].

Han, ZF ;

Uehira, S ;

Shinokubo, H ;

Oshima, K .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (23) :7854-7857

[12] Preparation of substituted allyl acetates and sulfones from Baylis-Hillman adducts in ionic liquid media [J].

Kabalka, GW ;

Venkataiah, B ;

Dong, G .

TETRAHEDRON LETTERS, 2003, 44 (25) :4673-4675

[13]

Kataoka T, 2000, ANGEW CHEM INT EDIT, V39, P2358, DOI 10.1002/1521-3773(20000703)39:13<2358::AID-ANIE2358>3.0.CO

[14]

2-Y

[15] THE CATALYTIC ASYMMETRIC ALDOL REACTION OF SILYL KETENE ACETALS WITH ALDEHYDES IN THE PRESENCE OF A CHIRAL BORANE COMPLEX - NITROETHANE AS A HIGHLY EFFECTIVE SOLVENT FOR CATALYTIC CONDITIONS [J].

KIYOOKA, S ;

KANEKO, Y ;

KUME, K .

TETRAHEDRON LETTERS, 1992, 33 (34) :4927-4930

[16] Asymmetric halo aldol reaction (AHA) [J].

Li, GG ;

Xu, X ;

Chen, DJ ;

Timmons, C ;

Carducci, MD ;

Headley, AD .

ORGANIC LETTERS, 2003, 5 (03) :329-331

[17]

Li GG, 2001, RRD ORG BIOORG CHEM, V4, P49

[18] The asymmetric catalytic aldol reaction of allenolates with aldehydes using N-fluoroacyl oxazaborolidine as the catalyst [J].

Li, GG ;

Wei, HX ;

Phelps, BS ;

Purkiss, DW ;

Kim, SH .

ORGANIC LETTERS, 2001, 3 (06) :823-826

[19] TiCl4-Mediated Baylis-Hillman and aldol reactions without the direct use of a Lewis base [J].

Li, GG ;

Wei, HX ;

Gao, JJ ;

Caputo, TD .

TETRAHEDRON LETTERS, 2000, 41 (01) :1-5

[20] Remarkable rate acceleration of imidazole-promoted Baylis-Hillman reaction involving cyclic enones in basic water solution [J].

Luo, SZ ;

Wang, PG ;

Cheng, JP .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (02) :555-558

← 1 2 3 4 →