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Carbonyls as Latent Alkyl Carbanions for Conjugate Additions
Author(s) -
Dai XiJie,
Wang Haining,
Li ChaoJun
Publication year - 2017
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.201700059
Subject(s) - nucleophile , chemistry , conjugate , ruthenium , carbanion , reagent , alkyl , catalysis , hydrazine (antidepressant) , combinatorial chemistry , organometallic chemistry , carbon fibers , organic chemistry , photochemistry , materials science , mathematical analysis , mathematics , chromatography , composite number , composite material
Abstract Conjugate addition of carbon nucleophiles to electron‐deficient olefins is one of the most powerful methods for forming carbon–carbon bonds. Despite great achievements in controlling the selectivity, variation of the carbon nucleophiles remains largely underexplored, with this approach relying mostly on organometallic reagents. Herein, we report that naturally abundant carbonyls can act as latent carbon nucleophiles for conjugate additions through a ruthenium‐catalyzed process, with water and nitrogen as innocuous byproducts. The key to our success is homogeneous ruthenium(II) catalysis, combined with phosphines as spectator ligands and hydrazine as the reducing agent. This chemistry allows the incorporation of highly functionalized alkyl fragments into a vast array of electron‐deficient olefins under mild reaction conditions in a reaction complementary to the classical organometallic‐reagent‐based conjugate additions mediated or catalyzed by “soft” transition metals.