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Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates
Author(s) -
Han Jung Tae,
Kim SeoungTae,
Baik MuHyun,
Yun Jaesook
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905361
Subject(s) - allylic rearrangement , stereocenter , nucleophile , chemistry , regioselectivity , olefin fiber , moiety , enantioselective synthesis , organic chemistry , catalysis , medicinal chemistry
Copper‐catalyzed stereoconvergent allylation of chiral sp 3 ‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing ( E )‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp 3 )‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee . Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent ( E )‐olefin formation from racemic allylic phosphates.