Intramolecular reactions of metal carbenoids with allylic ethers: is a free ylide involved in every case?

Clark, J. S. and Hansen, K. E. (2014) Intramolecular reactions of metal carbenoids with allylic ethers: is a free ylide involved in every case? Chemistry: A European Journal, 20(18), pp. 5454-5459. (doi:10.1002/chem.201304054) (PMID:24648216)

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Publisher's URL: http://dx.doi.org/10.1002/chem.201304054

Abstract

Rhodium-, copper- and iridium-catalyzed reactions of the 13C-labelled diazo carbonyl substrates 18* and 19* were performed. Results obtained from copper- and iridium-catalyzed reactions of the 13C -labelled α-diazo β-keto ester 19* indicate that either or both of these reactions do not proceed via a free oxonium ylide but instead follow a competing non-ylide route that delivers apparent [2,3]-sigmatropic rearrangement products. In the case of the iridium-catalyzed reaction of α-diazo β-keto ester 19*, results obtained from crossover experiments indicate that the initially formed metal-bound ylide dissociates to give an iridium enolate and an allyl cation, which recombine to form the C C bond.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Clark, Professor Stephen and Hansen, Miss Karin
Authors: Clark, J. S., and Hansen, K. E.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Publisher:Wiley-VCH Verlag
ISSN:0947-6539
ISSN (Online):1521-3765
Copyright Holders:Copyright © 2014 Wiley
First Published:First published in Chemistry: A European Journal 20(18):5454-5459
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher.

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