Metal-free reductive cleavage of C-O sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor.
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.
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, United Kingdom.
Sylvain P Y
SP
Cutulic
Neil J
NJ
Findlay
Sheng-Ze
SZ
Zhou
Ewan J T
EJ
Chrystal
John A
JA
Murphy