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Stereocontrol of All‐Carbon Quaternary Centers through Enantioselective Desymmetrization of Meso Primary Diols by Organocatalyzed Acyl Transfer
Author(s) -
Roux Christèle,
Candy Mathieu,
Pons JeanMarc,
Chuzel Olivier,
Bressy Cyril
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201308268
Subject(s) - desymmetrization , stereocenter , enantioselective synthesis , tetrahydropyran , kinetic resolution , chemistry , ring (chemistry) , catalysis , stereochemistry , asymmetric carbon , polyketide , organocatalysis , combinatorial chemistry , organic chemistry , optically active , biosynthesis , enzyme
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 C 6 F 6 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.