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Issue 22, 2012
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Computational studies on the mechanism of the gold(I)-catalysed rearrangement of cyclopropenes

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Density functional theory calculations have been employed to investigate the mechanism of gold(I)-catalysed rearrangements of cyclopropenes. Product formation is controlled by the initial ring-opening step which results in the formation of a gold-stabilised carbocation/gold carbene intermediate. With 3-phenylcyclopropene-3-methylcarboxylate, the preferred intermediate allows cyclisation via nucleophilic attack of the carbonyl group and hence butenolide formation. Further calculations on simple model systems show that substituent effects can be rationalised by the charge distribution in the ring-opening transition state and, in particular, a loss of negative charge at what becomes the β-position of the intermediate. With 1-C3H3R cyclopropenes (R = Me, vinyl, Ph), ring-opening therefore places the substituent at the β-position.

Graphical abstract: Computational studies on the mechanism of the gold(i)-catalysed rearrangement of cyclopropenes

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Publication details

The article was received on 24 Jan 2012, accepted on 29 Mar 2012 and first published on 04 May 2012

Article type: Paper
DOI: 10.1039/C2OB25183C
Citation: Org. Biomol. Chem., 2012,10, 4433-4440
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    Computational studies on the mechanism of the gold(I)-catalysed rearrangement of cyclopropenes

    M. S. Hadfield, L. J. L. Häller, A. Lee, S. A. Macgregor, J. A. T. O'Neill and A. M. Watson, Org. Biomol. Chem., 2012, 10, 4433
    DOI: 10.1039/C2OB25183C

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