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A Bimetallic Aluminum(salen) Complex for the Synthesis of 1,3-Oxathiolane-2-thiones and 1,3-Dithiolane-2-thiones

Lookup NU author(s): Professor William Clegg, Dr Ross Harrington, Professor Michael North, Dr Pedro Villuendas

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Abstract

The combined use of the bimetallic aluminum(salen) complex [Al(salen)](2)O and tetrabutylammonium bromide (or tributylamine) is found to catalyze the reaction between epoxides and carbon disulfide. In most cases, at 50 degrees C, the reaction produces 1,3-oxathiolane-2-thiones, while at 90 degrees C, 1,3-dithiolane-2-thiones are the main product. The structure and stereochemistry of three of the 1,3-dithiolane-2-thiones is unambiguously determined by X-ray crystallographic analysis, and this is used to correct errors in the literature concerning the synthesis of cyclic di- and trithiocarbonates. The kinetics of 1,3-oxathiolane-2-thione synthesis are determined, and the resulting rate equation, along with a stereochemical analysis of the reaction and catalyst modification studies, is used to determine a mechanism for the synthesis of 1,3-oxathiolane-2-thiones which contrasts with the mechanism previously determined for cyclic carbonate synthesis using the same bimetallic aluminum(salen) complex.

Publication metadata

Author(s): Clegg W, Harrington RW, North M, Villuendas P

Publication type: Article

Publication status: Published

Journal: Journal of Organic Chemistry

Year: 2010

Volume: 75

Issue: 18

Pages: 6201-6207

Print publication date: 01/09/2010

Date deposited: 01/12/2010

ISSN (print): 0022-3263

ISSN (electronic): 1520-6904

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/jo101121h

DOI: 10.1021/jo101121h

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