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

Supplementary files

Article information

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

Download Citation

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

Permissions

Request permissions

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Catalysis Science & Technology