A highly enantioselective 1,3-dipolar cycloaddition reaction in alcoholic media:: Ni(II)-pybox-tipsom catalyst

被引：36

作者：

Iwasa, S ^{[1
]}

Maeda, H ^{[1
]}

Nishiyama, K ^{[1
]}

Tsushima, S ^{[1
]}

Tsukamoto, Y ^{[1
]}

Nishiyama, H ^{[1
]}

机构：

[1] Toyohashi Univ Technol, Sch Mat Sci, Toyohashi, Aichi 4418580, Japan

来源：

TETRAHEDRON | 2002年 / 58卷 / 41期

关键词：

1,3-dipolar cycloaddition; molecular catalyst; nickel; nitrogen ligand; nitrogen heterocycle; nitrone;

D O I：

10.1016/S0040-4020(02)00978-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

From the viewpoint of environmentally friendly reaction conditions, catalytic asymmetric nitrone 1,3-dipolar cycloaddition (DC) reactions in protic media have been investigated. DC reaction of nitrones with alkenoyl oxazolidinone and pyrrolidinone derivatives in t-BuOH in the presence of sterically tuned bis(oxazolinyl)pyridine (pybox-tipsom 1d) and Ni(II) complex as a chiral Lewis acid catalyst proceeded smoothly to give the corresponding cycloadducts ranging from 90:10 to >99:1 of endo/exo ratio and ranging from 90 to 98% ee for the endo adduct. The use of sterically hindered alcohols such as t-BuOH and s-BuOH as a non-halogenated solvent was shown to effect rate acceleration for the DC reaction compare to CH2Cl2 at the same temperature. Furthermore, no solvolysis products of nitrones and cycloadducts were observed in these protic media despite the possible formation of Bronsted acid. (C) 2002 Elsevier Science Ltd. All rights reserved.

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页码：8281 / 8287

页数：7

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