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

doi:10.1039/C4SC00879K

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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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 language	English
Pages (from-to)	3651-3658
Number of pages	8
Journal	Chemical Science
Volume	5
Issue number	9
DOIs	https://doi.org/10.1039/C4SC00879K
Publication status	Published - 3 Jul 2014

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10.1039/C4SC00879K

Gould_2014_ChemSci_Catalyst
© Royal Society of Chemistry 2014. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
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Gould, E., Walden, D. M., Kasten, K., Johnston, R. C., Wu, J., Slawin, A. M. Z., Mustard, T. J. L., Johnston, B., Davies, T., Ha-Yeon Cheong, P., & Smith, A. D. (2014). Catalyst selective and regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates: synthetic and computational studies. Chemical Science, 5(9), 3651-3658. https://doi.org/10.1039/C4SC00879K

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

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.",

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

note = "The authors acknowledge the Royal Society for a University Research Fellowship (ADS) and the EPSRC and Merck Sharp \& Dohme Ltd (CASE award to EG) for funding, and the EPSRC National Mass Spectrometry Service Centre (Swansea). The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n° 279850.",

year = "2014",

month = jul,

day = "3",

doi = "10.1039/C4SC00879K",

language = "English",

volume = "5",

pages = "3651--3658",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "9",

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TY - JOUR

T1 - Catalyst selective and regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates

T2 - synthetic and computational studies

AU - Gould, Eoin

AU - Walden, Daniel M.

AU - Kasten, Kevin

AU - Johnston, Ryne C.

AU - Wu, Jiufeng

AU - Slawin, Alexandra M. Z.

AU - Mustard, Thomas J. L.

AU - Johnston, Brittany

AU - Davies, Tony

AU - Ha-Yeon Cheong, Paul

AU - Smith, Andrew D.

N1 - The authors acknowledge the Royal Society for a University Research Fellowship (ADS) and the EPSRC and Merck Sharp & Dohme Ltd (CASE award to EG) for funding, and the EPSRC National Mass Spectrometry Service Centre (Swansea). The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n° 279850.

PY - 2014/7/3

Y1 - 2014/7/3

N2 - 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.

AB - 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.

UR - http://www.rsc.org/suppdata/sc/c4/c4sc00879k/c4sc00879k1.pdf

UR - http://www.rsc.org/suppdata/sc/c4/c4sc00879k/c4sc00879k2.cif

UR - https://www.scopus.com/pages/publications/84962463383

U2 - 10.1039/C4SC00879K

DO - 10.1039/C4SC00879K

M3 - Article

SN - 2041-6520

VL - 5

SP - 3651

EP - 3658

JO - Chemical Science

JF - Chemical Science

IS - 9

ER -

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

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