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Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp 3 )−C(sp 3 ) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group
Author(s) -
KranidiotisHisatomi Nektarios,
Yi Hong,
Oestreich Martin
Publication year - 2021
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.202102233
Subject(s) - allylic rearrangement , stereocenter , electrophile , vinylsilane , chemistry , silylation , stereochemistry , medicinal chemistry , asymmetric induction , alkyl , catalysis , enantioselective synthesis , organic chemistry
A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed C(sp 3 )−C(sp 3 ) cross‐coupling of regioisomeric mixtures of racemic α‐/γ‐silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp 2 )−Si bond serves as a linchpin for the installation of various C(sp 3 ) substituents in a subsequent step.