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

Eoin Gould, Daniel M. Walden, Kevin Kasten, Ryne C. Johnston, Jiufeng Wu, Alexandra M. Z. Slawin, Thomas J. L. Mustard, Brittany Johnston, Tony Davies, Paul Ha-Yeon Cheong, Andrew D. Smith

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23 Citations (Scopus)
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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.

Original languageEnglish
Pages (from-to)3651-3658
Number of pages8
JournalChemical Science
Volume5
Issue number9
DOIs
Publication statusPublished - 3 Jul 2014

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