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Mechanism of Remote Conjugate Addition of a Lithium Organocuprate to a Polyconjugated Carbonyl Compound
Author(s) -
Yoshikai Naohiko,
Yamashita Tatsuya,
Nakamura Eiichi
Publication year - 2005
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.200501107
Subject(s) - conjugate , lithium (medication) , regioselectivity , conjugated system , chemistry , copper , density functional theory , combinatorial chemistry , computational chemistry , organic chemistry , catalysis , medicine , mathematical analysis , mathematics , endocrinology , polymer
Passing the buck : Rapid copper migration along the conjugated system results in regioselective remote conjugate addition of a lithium organocuprate to a polyenynyl carbonyl compound, as revealed by density‐functional calculations (see scheme). The unique structural/electronic properties of the σ/π‐allenyl–copper( III ) intermediates are responsible for the selective CC bond formation at the terminal acetylenic position.