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Regio‐ and Enantioselective Preparation of Chiral Allylic Sulfones Featuring Elusive Quaternary Stereocenters
Author(s) -
Cai Aijie,
Kleij Arjan W.
Publication year - 2019
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.201908318
Subject(s) - stereocenter , allylic rearrangement , enantioselective synthesis , phosphoramidite , desymmetrization , chemistry , steric effects , ligand (biochemistry) , combinatorial chemistry , catalysis , organic chemistry , receptor , dna , biochemistry , oligonucleotide
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.