Photocatalytic Cross-Pinacol Coupling Promoted by Carbon Dioxide.

Abstract

Cross-pinacol coupling of two different carbonyl compounds was achieved through successive one-electron transfer processes under photocatalytic conditions. In the reaction, an umpoled anionic carbinol synthon was generated in situ to react nucleophilically with a second electrophilic carbonyl compound. We revealed that a CO2 additive promoted the photocatalytic generation of the carbinol synthon to suppress undesired radical dimerization. A wide variety of aromatic and aliphatic carbonyl substrates underwent the cross-pinacol coupling to afford the corresponding unsymmetric vicinal 1,2-diols, where even a combination of carbonyl reactants with similar structures such as two aldehydes and two ketones were also well tolerated with high cross-coupling selectivity.