title: Carbonyls as Latent Alkyl Carbanions for Conjugate Additions.
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.
authors.affiliation: Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
authors.forename: Xi-Jie
authors.identifier: 0000-0002-4899-6359
authors.initials: XJ
authors.lastname: Dai
authors.affiliation: Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
authors.forename: Haining
authors.identifier: 0000-0002-9775-310X
authors.initials: H
authors.lastname: Wang
authors.affiliation: Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
authors.forename: Chao-Jun
authors.identifier: 0000-0002-3859-8824
authors.initials: CJ
authors.lastname: Li
keywords: carbonyls; conjugate addition; homogeneous catalysis; hydrazine; ruthenium