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Copper‐Catalyzed Enantioselective Allylic Alkylation with a γ‐Butyrolactone‐Derived Silyl Ketene Acetal
Author(s) -
Jette Carina I.,
Tong Z. Jaron,
Hadt Ryan G.,
Stoltz Brian M.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912618
Subject(s) - ketene , tsuji–trost reaction , allylic rearrangement , enantioselective synthesis , steric effects , chemistry , acetal , silylation , ligand (biochemistry) , alkylation , catalysis , aryl , medicinal chemistry , combinatorial chemistry , organic chemistry , biochemistry , alkyl , receptor
Herein, we report a Cu‐catalyzed enantioselective allylic alkylation using a γ‐butyrolactone‐derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono‐picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well‐tolerated. Spectroscopic studies reveal that a Cu I species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry.