The Silicon-Directed Tiffeneau–Demjanov Reaction:
Some Theoretical Studies
Melanie McClure A , Carl Schiesser A and 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).
Australian Journal of Chemistry 57(9) 869-876 https://doi.org/10.1071/CH04077
Submitted: 24 March 2004 Accepted: 20 July 2004 Published: 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.
[1]
J. B. Lambert,
Tetrahedron 1990, 46, 2677.
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[10]
[11]
