Stereocontrol of All‐Carbon Quaternary Centers through Enantioselective Desymmetrization of Meso Primary Diols by Organocatalyzed Acyl Transfer |
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Authors: | Christèle Roux Dr Mathieu Candy Prof Dr Jean‐Marc Pons Dr Olivier Chuzel Dr Cyril Bressy |
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Institution: | Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille (France) http://ism2.univ‐amu.fr/ |
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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. |
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Keywords: | desymmetrization meso compounds organocatalysis quaternary centers tetrahydropyranes |
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