Asymmetric synthesis of 3-substituted 3,4-dihydroisocoumarins via stereoselective addition of laterally lithiated chiral 2-(o-tolyl)oxazolines to aldehydes followed by diastereomer-selective lactonization

被引：31

作者：

Kurosaki, Y ^{[1
]}

Fukuda, T ^{[1
]}

Iwao, M ^{[1
]}

机构：

[1] Nagasaki Univ, Fac Engn, Dept Appl Chem, Nagasaki 8528521, Japan

来源：

TETRAHEDRON | 2005年 / 61卷 / 13期

关键词：

2-(o-tolyl)oxazoline; laterial lithiation; asymmetric synthesis; 3,4-dihydroisocoumarin; Ab initio calculation;

D O I：

10.1016/j.tet.2005.01.103

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Lateral lithiation of (S)-4-isopropyl-2-(o-tolyl)oxazoline in diethyl ether followed by the reaction with aldehydes in the presence of TMEDA produced the addition products with stereoselectivities up to 84% de. Utilization of TMEDA as a ligand is essential for the good selectivity. Rationale for the stereoselectivity is proposed based on ab initio calculation of the lateral lithio species. The major (S,S)-products lactonized faster than the minor (S,R)-products to the corresponding 3,4-dihydroisocoumarins under acidic conditions. Thus, (3S)-3,4-dihydroisocournarins were obtained in good optical purities up to 97% ee by sequential application of these matched stereoselective reactions. (c) 2005 Elsevier Ltd. All rights reserved.

引用

页码：3289 / 3303

页数：15

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