title: Reaction pathway of methylenation of carbonyl compounds with bis(iodozincio)methane.
abstract: About 40 years have passed since methylene dizinc reagent was discovered as a substitute for Wittig reagent. Density functional theory (DFT) calculations have been performed to understand the reaction pathways of methylenation of carbonyl compounds with bis(iodozincio)methane. The present computational/theoretical study concluded that the methylenation reaction with gem-dizinc reagent proceeds as a two-step reaction, that is, methylene addition (RDS) and olefination. In the first step, the nucleophilic attack of the CH2 group enhanced by two Zn proceeds under the assistance of the electrophilic activation of the carbonyl group with the Zn atom. In the second step, the olefination is facilitated by both Zn atoms of the gem-dizinc reagent without an electron transfer process.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoudai-katsura, Nishikyo, Kyoto 615-8510, Japan.
authors.forename: Mutsumi
authors.initials: M
authors.lastname: Sada
authors.forename: Shinsuke
authors.initials: S
authors.lastname: Komagawa
authors.forename: Masanobu
authors.initials: M
authors.lastname: Uchiyama
authors.forename: Masami
authors.initials: M
authors.lastname: Kobata
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Mizuno
authors.forename: Kiitiro
authors.initials: K
authors.lastname: Utimoto
authors.forename: Koichiro
authors.initials: K
authors.lastname: Oshima
authors.forename: Seijiro
authors.initials: S
authors.lastname: Matsubara
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D007202:Indicators and Reagents; D007659:Ketones / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D000447:Aldehydes; D000475:Alkenes; D002264:Carboxylic Acids; D007202:Indicators and Reagents; D007659:Ketones; C513531:bis(iodozincio)methane; D008697:Methane