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Nucleophile Coordination Enabled Regioselectivity in Palladium‐Catalyzed Asymmetric Allylic C−H Alkylation
Author(s) -
Fan LianFeng,
Luo ShiWei,
Chen ShuSen,
Wang TianCi,
Wang PuSheng,
Gong LiuZhu
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908960
Subject(s) - nucleophile , regioselectivity , tsuji–trost reaction , chemistry , enantioselective synthesis , palladium , allylic rearrangement , phosphoramidite , catalysis , selectivity , alkylation , medicinal chemistry , stereochemistry , combinatorial chemistry , organic chemistry , dna , biochemistry , oligonucleotide
Branched selectivity in asymmetric allylic C−H alkylation is enabled by using 2‐acylimidazoles as nucleophiles in the presence of a chiral phosphoramidite‐palladium catalyst. A wide range of terminal alkenes, including 1,4‐dienes and allylarenes, are nicely tolerated and provide chiral 2‐acylimidazoles in moderate to high yields and with high levels of regio‐, and enantio‐, and E / Z ‐selectivities. Mechanistic studies using density‐functional theory calculations suggest a nucleophile‐coordination‐enabled inner‐sphere attack mode for the enantioselective carbon–carbon bond‐forming event.