Diastereoselective Inter- and Intramolecular Pinacol Coupling of Aldehydes Promoted by Monomeric Titanocene(III) Complex Cp₂TiPh

Abstract

A monomeric titanocene(III) derivative, Cp(2)TiPh, effectively promoted the pinacol coupling of both an aromatic aldehyde, benzaldehyde, and an aliphatic aldehyde, 3-phenylpropionaldehyde. The same reactive complex was successfully generated by a catalytic amount of a precursor, Cp(2)Ti(Ph)Cl, and its stoichiometric amount of Zn. The Cp(2)TiPh-catalyzed pinacol coupling of benzaldehyde derivatives and aliphatic aldehydes afforded the corresponding 1,2-diols in high yields with moderate to good threo-selectivity. On the other hand, Cp(2)TiPh-catalyzed pinacol cyclization of dials gave cyclic 1,2-diols with excellent diastereoselectivity. The extension of this protocol to chiral dials demonstrated that the phenyltitanium complex catalytically transmitted an axial chirality or a central chirality of the starting dials to the central chirality of the resultant 1,2-diols.