Regio‐ and Enantioselective Preparation of Chiral Allylic Sulfones Featuring Elusive Quaternary Stereocenters. (19th September 2019)

• Record Type: Journal Article
• Authors: Cai, Aijie; Kleij, Arjan W.
• Is Part Of: Angewandte Chemie. Volume 131:Number 42(2019)
• Page Start: 15086
• Page End: 15091
• Publication Date: 2019-09-19
• Subjects: Allylsulfone -- Enantioselektivität -- Homogene Katalyse -- Palladium -- Regioselektivität; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201908318
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We describe here the first general asymmetric synthesis of sterically encumbered α, α‐disubstituted allylic sulfones via Pd‐catalyzed allylic substitution. The design and application of a new and highly efficient phosphoramidite ligand (L10 ) proved to be crucial, and a wide variety of challenging allylic sulfones featuring quaternary stereocenters could be obtained in good yields and with good to excellent levels of regio‐ and enantioselectivities under attractive process conditions. The developed methodology employs easily accessible chemical feedstock including racemic allylic precursors and sodium sulfinates. The utility of the method is further demonstrated by the synthesis of the sesquiterpene (−)‐Agelasidine A. Abstract : Chirale Sulfone schreiten voran : Die erste allgemeine Pd‐katalysierte asymmetrische Synthese von α, α‐disubstituierten Allylsulfonen wurde realisiert. Das Verfahren basiert auf einer Tsuji‐Trost‐Allylalkylierung unter Verwendung von Alkyl‐ und Arylsulfinat‐Nukleophilen und einem neuen Phosphoramiditliganden und wurde erfolgreich auf die formale Synthese des Sesquiterpens (−)‐Agelasidin A angewendet.