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Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
Author(s) -
Akiyama Sota,
Kubota Koji,
Mikus Malte S.,
Paioti Paulo H. S.,
Romiti Filippo,
Liu Qinghe,
Zhou Yuebiao,
Hoveyda Amir H.,
Ito Hajime
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.201906283
Subject(s) - enantioselective synthesis , stereocenter , allylic rearrangement , aldimine , yield (engineering) , chemistry , catalysis , enantiomer , fluoride , organic chemistry , stereochemistry , inorganic chemistry , materials science , metallurgy
The first catalytic method for diastereo‐ and enantioselective synthesis of allylic boronates bearing a Z ‐trisubstituted alkenyl fluoride is disclosed. Boryl substitution is performed with either a Z ‐ or E ‐allyldifluoride and is catalyzed by bisphosphine/Cu complexes, affording products in up to 99 % yield with >98:2 Z / E selectivity and 99:1 enantiomeric ratio. A variety of subsequent modifications are feasible, and notable examples are diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containing a fluorosubstituted stereogenic quaternary center.