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Royal Society of Chemistry, Chemical Science, 9(5), p. 3651

DOI: 10.1039/c4sc00879k

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

Journal article published in 2014 by Eoin Gould, Daniel M. Walden, Kevin Kasten, Ryne C. Johnston ORCID, Jiufeng Wu, Alexandra M. Z. Slawin ORCID, Thomas J. L. Mustard, Brittany Johnston, Tony Davies, Paul Ha-Yeon Cheong, Paul Ha-Yeon Cheong, Andrew D. Smith
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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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.