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Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes

Marsden, S.P. and Ducept, P.C. (2005) Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes. Beilstein Journal of Organic Chemistry, 1 (5). ISSN 1860-5397

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Abstract

BACKGROUND: Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes prepared through rhodium(II)-mediated rearrangement of silylated diazoketones.

RESULTS: A range of novel 1,3-disubstituted and 1,3,3-trisubstituted allenylsilanes were prepared using stabilised and semi-stabilised ylides. Alkylidenation with non-stabilised phosphorus ylides was not viable, but the use of titanium-based methylenating reagents was successful, allowing access to 1-substituted allenylsilanes.

CONCLUSION: Many novel allenylsilanes may be accessed by alkylidenation of substituted silylketenes. Importantly, for the first time, simple methylenation of silylketenes has been achieved using titanium carbenoid-based reagents.

Item Type: Article
Copyright, Publisher and Additional Information: © 2005 Marsden and Ducept; licensee Beilstein-Institut. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Institution: The University of Leeds
Academic Units: The University of Leeds > Faculty of Maths and Physical Sciences (Leeds) > School of Chemistry (Leeds)
Depositing User: Sherpa Assistant
Date Deposited: 06 Jan 2006
Last Modified: 07 Jun 2014 09:17
Published Version: http://bjoc.beilstein-journals.org/content/1/1/5
Status: Published
Refereed: Yes
Identification Number: 10.1186/1860-5397-1-5
URI: http://eprints.whiterose.ac.uk/id/eprint/924

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