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Updated: Feb 15, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes
R J Schwamm1, M Lein, M P Coles
1School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington 6012, New Zealand. martyn.coles@vuw.ac.nz.
Abstract:
Bismuth(iii) TEMPOxide compounds have been synthesized from the coupling of Bi(ii) species with the TEMPO˙ radical. The steric profile of the supporting bis(amido)disiloxane ligand promotes different fluxional behaviour in solution, and DFT calculations suggest variation in the Bi-O bond character. These compounds are active catalysts for oxidative coupling of TEMPO and silane substrates, believed to proceed via metathesis of Bi-O and Si-H bonds followed by decomposition of bismuth-hydride intermediate species.
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