The Silicon-Directed Tiffeneau–Demjanov Reaction: Some Theoretical Studies

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Contents Vol 57(9)

doi:10.1071/CH04077

The Silicon-Directed Tiffeneau–Demjanov Reaction:
Some Theoretical Studies

Melanie McClure ^A, Carl Schiesser ^A, Jonathan White ^B

^A School of Chemistry, University of Melbourne, Parkville VIC 3010, Australia.
^B Author to whom correspondence should be addressed (e-mail: whitejm@unimelb.edu.au).





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Australian Journal of Chemistry 57(9) 869–876 http://dx.doi.org/10.1071/CH04077
Submitted: 24 March 2004 Accepted: 20 July 2004 Published online: 1 September 2004

Abstract

The Tiffeneau–Demjanov chain extension reaction was modelled using the B3LYP/6-31G* basis set for both diazonium and water leaving groups. The chain extension of 12 with the diazonium leaving group occurs with an early transition state, a low activation barrier, and very little participation by the silicon substituent. Chain extension of 15, involving displacement of the less reactive leaving group water, occurs with a later transition state, a significantly higher activation barrier, and with greater participation by the silicon substituent.