title: Palladium(II)-Catalyzed Dehydroboration via Generation of Boron Enolates.
abstract: The PdII-catalyzed dehydroboration of boron enolates generated from ketones and 9-iodo-9-borabicyclo[3.3.1]nonane was achieved, providing a synthetically versatile protocol from ketones to α,β-unsaturated ketones. The PdIIcompound employed in this reaction worked catalytically in the presence of Cu(OAc)2. The high trans-selectivity of the olefinic moiety was observed. Aryl halide moieties (-Br and -Cl) remained intact for this reaction in spite of the presence of a Pd species. An ester substrate could also be applied when a stoichiometric amount of PdIIwas used. The crossover reactions using boron and silyl enolates revealed that the oxidation reaction is much faster than the Saegusa-Ito reaction.
authors.affiliation: The Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka, 567-0047, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Sakamoto
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka, 565-0871, Japan.
authors.forename: Toru
authors.initials: T
authors.lastname: Amaya
authors.affiliation: The Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka, 567-0047, Japan.
authors.forename: Takeyuki
authors.initials: T
authors.lastname: Suzuki
authors.affiliation: The Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka, 567-0047, Japan.
authors.forename: Toshikazu
authors.initials: T
authors.lastname: Hirao
keywords: boron enolate; dehydrogenation; enones; oxidation; palladium