Issue 17, 2020

Chemoselective oxidative addition of vinyl sulfones mediated by palladium complexes bearing picolyl-N-heterocyclic carbene ligands.

Abstract

The manifold interactions of (E)- or (Z)-1,2-ditosylethene with a palladium(0) centre bearing picolyl-NHC carbene ligands have been studied thoroughly. (E)-1,2-Ditosylethene produces the expected and stable η2-olefin palladium complexes, whereas the coordination of the Z derivative alternatively promotes the isomerization of the olefin itself or an oxidative addition process depending on the steric bulkiness of carbene substituents and/or the adopted synthetic procedure. Remarkably, the oxidative addition pathway involves a selective S-vinyl (not S-aryl) breaking and produces selectively the S- rather than O-coordinated sulfinate. A mechanistic study has clarified the reasons of the chemoselectivity of the process, which was proved to be kinetically controlled. All the involved species have been isolated and exhaustively characterized. In particular, we report the first example of the X-ray crystal structure of a complex bearing one vinyl and one S-sulfinate fragment coordinated to palladium.

Graphical abstract: Chemoselective oxidative addition of vinyl sulfones mediated by palladium complexes bearing picolyl-N-heterocyclic carbene ligands.

Supplementary files

Article information

Article type
Paper
Submitted
26 Mar 2020
Accepted
08 Apr 2020
First published
09 Apr 2020

Dalton Trans., 2020,49, 5684-5694

Chemoselective oxidative addition of vinyl sulfones mediated by palladium complexes bearing picolyl-N-heterocyclic carbene ligands.

T. Scattolin, C. Santo, N. Demitri, L. Canovese and F. Visentin, Dalton Trans., 2020, 49, 5684 DOI: 10.1039/D0DT01144D

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