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Issue 9, 2014
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Catalyst selective and regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates: synthetic and computational studies

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Abstract

The regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates is described, with DMAP giving preferential N-carboxylation and triazolinylidenes promoting selective C-carboxylation (both with up to >99 : 1 regioselectivity). An enantioselective O- to C-carboxyl variant using NHC catalysis is demonstrated (up to 92% ee), while mechanistic and DFT studies outline the pathways operative in this system and provide insight into the reasons for the observed selectivity.

Graphical abstract: Catalyst selective and regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates: synthetic and computational studies

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Publication details

The article was received on 25 Mar 2014, accepted on 06 Jun 2014 and first published on 03 Jul 2014


Article type: Edge Article
DOI: 10.1039/C4SC00879K
Citation: Chem. Sci., 2014,5, 3651-3658
  • Open access: Creative Commons BY license
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    Catalyst selective and regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates: synthetic and computational studies

    E. Gould, D. M. Walden, K. Kasten, R. C. Johnston, J. Wu, A. M. Z. Slawin, T. J. L. Mustard, B. Johnston, T. Davies, P. Ha-Yeon Cheong and A. D. Smith, Chem. Sci., 2014, 5, 3651
    DOI: 10.1039/C4SC00879K

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