title: Rhenium-catalyzed anti-Markovnikov addition reaction of methanetricarboxylates to unactivated terminal acetylenes.
abstract: A novel anti-Markovnikov addition reaction of methanetricarboxylates with terminal acetylenes under neutral conditions was achieved using a rhenium complex. This transformation represents a rare example of intermolecular anti-Markovnikov addition of carbon nucleophiles to unactivated terminal acetylenes. 1,3-Diesters having bulky substituents at the active methylene carbon are also applicable as substrates to provide anti-Markovnikov adducts as single regio- and stereoisomers. Preliminary mechanistic studies imply that the rhenium vinylidene species is the key intermediate in the current catalytic cycle.
authors.affiliation: Division of Chemistry and Biotechnology, Graduate School of Natural Science and Technology and ‡Research Center of New Functional Materials for Energy Production, Storage and Transport, Okayama University , 3-1-1 Tsushimanaka, Kita-ku, Okayama, 700-8530, Japan.
authors.forename: Shunsuke
authors.initials: S
authors.lastname: Hori
authors.forename: Masahito
authors.initials: M
authors.lastname: Murai
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Takai