A synthetic method for conducting the acyloin reaction using electron transfer in solution is reported. By linking two esters via their oxygen atoms, it was possible to perform crossed acyloin reactions between two different ester functionalities and display a high degree of preference for an intramolecular coupling process.

Exerting Control over the Acyloin Reaction. -The acyloin reaction of unsymmetrical diesters (V) leads regioselectively to derivatives (VI) in good yields. Acyloin (VIc) is used as convenient starting compound for the synthesis of diols (VII) and (IX), thiazole (XI), and indole (XIII). -(DONOHOE*, T. J.; JAHANSHAHI, A.; TUCKER, M. J.; BHATTI, F. L.; ROSLAN, I. A.; KABESHOV, M.; WRIGLEY, G.; Chem. Commun. (Cambridge) 47 (2011) 20, 5849-5851, http://dx.doi.org/10.1039/c1cc11654a ; Chem. Res. Lab., Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -R. Staver 34-026