title: Highly Enantioselective Acylation of Acyclic Meso 1,3-Diols through Synergistic Isothiourea-Catalyzed Desymmetrization/Chiroablative Kinetic Resolution.
abstract: A general and highly efficient organocatalyzed desymmetrization of acyclic meso 1,3-diols through acyl transfer using chiral isothioureas is described. The introduction of π-systems in the acyclic substrates provided new opportunities in terms of reactivity, enantioselectivity and synthetic potential. To reach this high level of enantioselectivity (up to er >99:1), the reaction proceeds through a synergistic mechanism involving a desymmetrization reaction and a chiroablative kinetic resolution process. This methodology was used with success as the sole enantioselective catalytic step (developed on a gram scale) to achieve the total synthesis of the antiosteoporotic diarylheptanoid (-)-diospongin A (7 steps).
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Jérémy
authors: J
authors: Merad
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Prashant
authors: P
authors: Borkar
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Tracy
authors: T
authors: Bouyon Yenda
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Christèle
authors: C
authors: Roux
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Jean-Marc
authors: JM
authors: Pons
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Jean-Luc
authors: JL
authors: Parrain
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Olivier
authors: O
authors: Chuzel
authors: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors: Cyril
authors: C
authors: Bressy
mesh_terms: D000215:Acylation; D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D036381:Diarylheptanoids / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D011714:Pyrans; D013237:Stereoisomerism; D013890:Thiourea / Q000737:chemistry*
chemical_list: D000438:Alcohols; D036381:Diarylheptanoids; D011714:Pyrans; C521317:diospongin A; D013890:Thiourea