title: Stereocontrol of all-carbon quaternary centers through enantioselective desymmetrization of meso primary diols by organocatalyzed acyl transfer.
abstract: The symmetry breaking of meso primary diols bearing a tetrahydropyran ring was employed, using catalytic asymmetric acyl transfer, to control all-carbon quaternary stereocenters. The planar chiral Fu DMAP catalyst was used in this reaction to reach a high degree of enantioselectivity (up to 97:3 e.r.) through a synergic effect combining a desymmetrization step and a kinetic resolution. Moreover, a beneficial effect was exhibited by C6F6 solvent, yielding the first example of an organocatalyzed asymmetric acyl transfer. The desymmetrized monoesters were then used to obtain, after a straightforward ring opening sequence, complex polyketide building blocks bearing all-carbon quaternary stereocenters.
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille (France) http://ism2.univ-amu.fr/
authors: Christèle
authors: C
authors: Roux
authors: Mathieu
authors: M
authors: Candy
authors: Jean-Marc
authors: JM
authors: Pons
authors: Olivier
authors: O
authors: Chuzel
authors: Cyril
authors: C
authors: Bressy
keywords: desymmetrization; meso compounds; organocatalysis; quaternary centers; tetrahydropyranes