An experimental and theoretical study into the facile, homogenous (N-heterocyclic carbene)2-Pd(0) catalyzed diboration of internal and terminal alkynes

Melvyn B. Ansell; Vitor H. Menezes da Silva; Gabriel Heerdt; Ataualpa A. C. Braga; John Spencer; Oscar Navarro

doi:10.1039/C6CY01266C

An experimental and theoretical study into the facile, homogenous (N-heterocyclic carbene)₂-Pd(0) catalyzed diboration of internal and terminal alkynes†

Melvyn B. Ansell,^a Vitor H. Menezes da Silva,^b Gabriel Heerdt,

^bc Ataualpa A. C. Braga,*^b John Spencer*^a and Oscar Navarro*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Sussex, Brighton, UK
E-mail: j.spencer@sussex.ac.uk, o.navarro@sussex.ac.uk

^b Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, Avenida Professor Lineu Prestes, 748, São Paulo, Brazil
E-mail: ataualpa@iq.usp.br

^c Instituto de Química, Universidade Estadual de Campinas, CP 6154, Campinas-SP, Brazil

Abstract

Pd(ITMe)₂(PhC [triple bond, length as m-dash] CPh) acts as a highly reactive pre-catalyst in the unprecedented homogenous catalyzed diboration of terminal and internal alkynes, yielding a number of novel and known syn-1,2-diborylalkenes in a 100% stereoselective manner. DFT calculations suggest that a similar reaction pathway to that proposed for platinum phosphine analogues is followed, and that destabilization of key intermediates by the NHCs is vital to the overall success for the palladium-catalyzed B–B addition to alkynes.

This article is part of the themed collection: SBQ-RSC: Celebrating UK-Brazil collaborations

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Article information

DOI: https://doi.org/10.1039/C6CY01266C
Article type: Paper
Submitted: 10 6 2016
Accepted: 18 8 2016
First published: 19 8 2016
This article is Open Access

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Catal. Sci. Technol., 2016,6, 7461-7467

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An experimental and theoretical study into the facile, homogenous (N-heterocyclic carbene)₂-Pd(0) catalyzed diboration of internal and terminal alkynes

M. B. Ansell, V. H. Menezes da Silva, G. Heerdt, A. A. C. Braga, J. Spencer and O. Navarro, Catal. Sci. Technol., 2016, 6, 7461 DOI: 10.1039/C6CY01266C

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Catalysis Science & Technology