Mechanistic study of the Soai autocatalytic reaction informed by kinetic analysis

被引：52

作者：

Blackmond, DG ^{[1
]}

机构：

[1] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AZ, England

来源：

TETRAHEDRON-ASYMMETRY | 2006年 / 17卷 / 04期

关键词：

D O I：

10.1016/j.tetasy.2006.01.012

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Detailed kinetic studies of the Soai reaction affirm the basic mechanistic picture previously developed in kinetic, spectroscopic and molecular modelling studies, and also suggest that refinements to the proposed elementary reaction steps must be considered. The alkanol reaction product is driven strongly and without bias towards the formation of homochiral and heterochiral dimers. The reaction is catalyzed by only the homochiral dimers. Consideration of the kinetic profiles from reactions carried out with different initial dialkylzinc concentrations support a proposal for a tetrameric transition state, but further experimental work is required to delineate the nature of this species. The power of reaction calorimetry as a kinetic tool for discerning subtle effects of the shape of the kinetic profile is highlighted. The importance of combining kinetic evidence with spectroscopic and other characterization tools is emphasized. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：584 / 589

页数：6

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