title: Exclusive selectivity in the one-pot formation of C-C and C-Se bonds involving Ni-catalyzed alkyne hydroselenation: optimization of the synthetic procedure and a mechanistic study.
abstract: A unique Ni-catalyzed transformation is reported for the one-pot highly selective synthesis of previously unknown monoseleno-substituted 1,3-dienes starting from easily available terminal alkynes and benzeneselenol. The combination of a readily available catalyst precursor, Ni(acac)2, and an appropriately tuned phosphine ligand, PPh2Cy, resulted in the exclusive assembly of the s-gauche diene skeleton via the selective formation of C-C and C-Se bonds. The unusual diene products were stable under regular experimental conditions, and the products maintained the s-gauche geometry both in the solid state and in solution, as confirmed by X-ray analysis and NMR spectroscopy. Thorough mechanistic studies using ESI-MS revealed the key Ni-containing species involved in the reaction.
authors.affiliation: Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences , Leninsky Prospect 47, Moscow 119991, Russia.
authors.forename: Nikolay V
authors.initials: NV
authors.lastname: Orlov
authors.forename: Igor V
authors.initials: IV
authors.lastname: Chistyakov
authors.forename: Levon L
authors.initials: LL
authors.lastname: Khemchyan
authors.forename: Valentine P
authors.initials: VP
authors.lastname: Ananikov
authors.forename: Irina P
authors.initials: IP
authors.lastname: Beletskaya
authors.forename: Zoya A
authors.initials: ZA
authors.lastname: Starikova