Low-Coordinate NHC-Zinc Hydride Complexes Catalyze Alkyne C-H Borylation and Hydroboration Using Pinacolborane

Richard J. Procter; Marina Uzelac; Jessica Cid; Philip J. Rushworth; Michael J. Ingleson

doi:10.1021/acscatal.9b01370

Low-Coordinate NHC-Zinc Hydride Complexes Catalyze Alkyne C-H Borylation and Hydroboration Using Pinacolborane

Richard J. Procter, Marina Uzelac, Jessica Cid, Philip J. Rushworth, Michael J. Ingleson

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

98 Citations (SciVal)

Abstract

Organozinc compounds containing sp, sp², and sp³ C-Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn-H species and organoboronate esters (RBPin). This Zn-C/H-B metathesis step is key to enabling zinc-catalyzed borylation reactions, and it is used in this work to develop both terminal alkyne C-H borylation and internal alkyne hydroboration. These two conversions can be combined in one pot to achieve the zinc-catalyzed conversion of terminal alkynes to 1,1-diborylated alkenes without isolation of the sensitive (to protodeboronation) alkynyl boronate ester intermediates. Mechanistic studies involving the isolation of intermediates, stoichiometric experiments, and DFT calculations all support mechanisms involving organozinc species that undergo metathesis with HBPin. Furthermore, zinc-catalyzed hydroboration can proceed via a hydrozincation step, which does not require any exogenous catalyst in contrast to all previously reported alkyne hydrozincations. Bulky N-heterocyclic carbenes (NHCs) are key for effective catalysis as the NHC steric bulk enhances the stability of the NHC-Zn species present during catalysis and provides access to low-coordinate (NHC)Zn-H cations that are electrophilic yet Brønsted basic. This work provides an alternative approach to access synthetically desirable pinacol-organoboronate esters using earth-abundant metal-based borylation catalysts.

Original language	English
Pages (from-to)	5760-5771
Number of pages	12
Journal	ACS Catalysis
Volume	9
Issue number	6
Early online date	15 May 2019
DOIs	https://doi.org/10.1021/acscatal.9b01370
Publication status	Published - 7 Jun 2019

Bibliographical note

Funding Information:
*E-mail: [email protected]. ORCID Michael J. Ingleson: 0000-0001-9975-8302 Author Contributions ∥R.J.P. and M.U. contributed equally to the experimental sections of this work, while J.C. performed the DFT calculations. Funding EPSRC and GSK (Case Award to R.J.P.) European Research Council (769599). Notes The authors declare no competing financial interest.

Funding Information:
This work was made possible by financial support from the EPSRC and GSK (Case Award to R.J.P.) and the Horizon 2020 Research and Innovation Program (Grant No. 769599). Prof. Richard Layfield is thanked for useful discussions.

Publisher Copyright:
© Copyright 2019 American Chemical Society.

Funding

*E-mail: [email protected]. ORCID Michael J. Ingleson: 0000-0001-9975-8302 Author Contributions ∥R.J.P. and M.U. contributed equally to the experimental sections of this work, while J.C. performed the DFT calculations. Funding EPSRC and GSK (Case Award to R.J.P.) European Research Council (769599). Notes The authors declare no competing financial interest. This work was made possible by financial support from the EPSRC and GSK (Case Award to R.J.P.) and the Horizon 2020 Research and Innovation Program (Grant No. 769599). Prof. Richard Layfield is thanked for useful discussions.

Keywords

borylation
homogeneous catalysis
hydrides
N-heterocyclic carbene
zinc

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.9b01370

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title = "Low-Coordinate NHC-Zinc Hydride Complexes Catalyze Alkyne C-H Borylation and Hydroboration Using Pinacolborane",

abstract = "Organozinc compounds containing sp, sp2, and sp3 C-Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn-H species and organoboronate esters (RBPin). This Zn-C/H-B metathesis step is key to enabling zinc-catalyzed borylation reactions, and it is used in this work to develop both terminal alkyne C-H borylation and internal alkyne hydroboration. These two conversions can be combined in one pot to achieve the zinc-catalyzed conversion of terminal alkynes to 1,1-diborylated alkenes without isolation of the sensitive (to protodeboronation) alkynyl boronate ester intermediates. Mechanistic studies involving the isolation of intermediates, stoichiometric experiments, and DFT calculations all support mechanisms involving organozinc species that undergo metathesis with HBPin. Furthermore, zinc-catalyzed hydroboration can proceed via a hydrozincation step, which does not require any exogenous catalyst in contrast to all previously reported alkyne hydrozincations. Bulky N-heterocyclic carbenes (NHCs) are key for effective catalysis as the NHC steric bulk enhances the stability of the NHC-Zn species present during catalysis and provides access to low-coordinate (NHC)Zn-H cations that are electrophilic yet Br{\o}nsted basic. This work provides an alternative approach to access synthetically desirable pinacol-organoboronate esters using earth-abundant metal-based borylation catalysts.",

keywords = "borylation, homogeneous catalysis, hydrides, N-heterocyclic carbene, zinc",

author = "Procter, {Richard J.} and Marina Uzelac and Jessica Cid and Rushworth, {Philip J.} and Ingleson, {Michael J.}",

note = "Funding Information: *E-mail: [email protected]. ORCID Michael J. Ingleson: 0000-0001-9975-8302 Author Contributions ∥R.J.P. and M.U. contributed equally to the experimental sections of this work, while J.C. performed the DFT calculations. Funding EPSRC and GSK (Case Award to R.J.P.) European Research Council (769599). Notes The authors declare no competing financial interest. Funding Information: This work was made possible by financial support from the EPSRC and GSK (Case Award to R.J.P.) and the Horizon 2020 Research and Innovation Program (Grant No. 769599). Prof. Richard Layfield is thanked for useful discussions. Publisher Copyright: {\textcopyright} Copyright 2019 American Chemical Society.",

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AU - Cid, Jessica

AU - Rushworth, Philip J.

AU - Ingleson, Michael J.

N1 - Funding Information: *E-mail: [email protected]. ORCID Michael J. Ingleson: 0000-0001-9975-8302 Author Contributions ∥R.J.P. and M.U. contributed equally to the experimental sections of this work, while J.C. performed the DFT calculations. Funding EPSRC and GSK (Case Award to R.J.P.) European Research Council (769599). Notes The authors declare no competing financial interest. Funding Information: This work was made possible by financial support from the EPSRC and GSK (Case Award to R.J.P.) and the Horizon 2020 Research and Innovation Program (Grant No. 769599). Prof. Richard Layfield is thanked for useful discussions. Publisher Copyright: © Copyright 2019 American Chemical Society.

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N2 - Organozinc compounds containing sp, sp2, and sp3 C-Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn-H species and organoboronate esters (RBPin). This Zn-C/H-B metathesis step is key to enabling zinc-catalyzed borylation reactions, and it is used in this work to develop both terminal alkyne C-H borylation and internal alkyne hydroboration. These two conversions can be combined in one pot to achieve the zinc-catalyzed conversion of terminal alkynes to 1,1-diborylated alkenes without isolation of the sensitive (to protodeboronation) alkynyl boronate ester intermediates. Mechanistic studies involving the isolation of intermediates, stoichiometric experiments, and DFT calculations all support mechanisms involving organozinc species that undergo metathesis with HBPin. Furthermore, zinc-catalyzed hydroboration can proceed via a hydrozincation step, which does not require any exogenous catalyst in contrast to all previously reported alkyne hydrozincations. Bulky N-heterocyclic carbenes (NHCs) are key for effective catalysis as the NHC steric bulk enhances the stability of the NHC-Zn species present during catalysis and provides access to low-coordinate (NHC)Zn-H cations that are electrophilic yet Brønsted basic. This work provides an alternative approach to access synthetically desirable pinacol-organoboronate esters using earth-abundant metal-based borylation catalysts.

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KW - N-heterocyclic carbene

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Low-Coordinate NHC-Zinc Hydride Complexes Catalyze Alkyne C-H Borylation and Hydroboration Using Pinacolborane

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

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