Metal-free reductive cleavage of C-O sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor

Sylvain P Y Cutulic; Neil J Findlay; Sheng-Ze Zhou; Ewan J T Chrystal; John A Murphy

doi:10.1021/jo901815t

Metal-free reductive cleavage of C-O sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor

J Org Chem. 2009 Nov 20;74(22):8713-8. doi: 10.1021/jo901815t.

Authors

Sylvain P Y Cutulic¹, Neil J Findlay, Sheng-Ze Zhou, Ewan J T Chrystal, John A Murphy

Affiliation

¹ WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, United Kingdom.

PMID: 19845372
DOI: 10.1021/jo901815t

Abstract

Neutral organic electron-donor 7, formally a pyridinylidene carbene dimer, effects reductive cleavage of C-O sigma-bonds in acyloin derivatives Ar(CO)CRR'OX (X = OAc, OPiv, OBz, OMs) and this represents the first cleavage of C-O sigma-bonds by a neutral organic electron-donor. The methodology is applicable to a large array of substrates and the reduced counterparts were isolated in good to excellent yields. For certain substrates, donor 7 behaves as a base, effecting condensation reactions with some acetate ester derivatives of acyloins, leading to butenolides. The variation in reactivity among the different substrates was rationalized.