Ligand-Controlled regioselectivity in the hydrothiolation of alkynes by rhodium N-heterocyclic carbene catalysts
Autores: Andrea Di Giuseppe, Ricardo Castarlenas, Jesús J. Pérez-Torrente, Marcelo Crucianelli, Victor Polo, Rodrigo Sancho, Fernando J. Lahoz y Luis Oro
Ref. revista: Journal of the American Chemical Society, 134, 8171-8183 (2012)
Rh−N-heterocyclic carbene compounds [Rh(μ-Cl)(IPr)(η2-olefin)]2 and RhCl(IPr)(py)(η2-olefin) (IPr = 1,3-
bis(2,6-diisopropylphenyl)imidazol-2-carbene, py = pyridine, olefin = cyclooctene or ethylene) are highly active catalysts for
alkyne hydrothiolation under mild conditions. A regioselectivity switch from linear to 1-substituted vinyl sulfides was observed
when mononuclear RhCl(IPr)(py)(η2-olefin) catalysts were used instead of dinuclear precursors. A complex interplay between electronic and steric effects exerted by IPr, pyridine, and hydride ligands accounts for the observed regioselectivity. Both IPr and pyridine ligands stabilize formation of square-pyramidal thiolate−hydride active species in which the encumbered and powerful electron-donor IPr ligand directs coordination of pyridine trans to it, consequently blocking access of the incoming alkyne in this position. Simultaneously, the higher trans director hydride ligand paves the way to a cis thiolate−alkyne disposition, favoring formation of 2,2-disubstituted metal−alkenyl species and subsequently the Markovnikov vinyl sulfides via alkenyl−hydride reductive elimination. DFT calculations support a plausible reaction pathway where migratory insertion of the alkyne into the rhodium−thiolate bond is the rate-determining step.
Rh−N-heterocyclic carbene compounds [Rh(μ-Cl)(IPr)(η2-olefin)]2 and RhCl(IPr)(py)(η2-olefin) (IPr = 1,3-
bis(2,6-diisopropylphenyl)imidazol-2-carbene, py = pyridine, olefin = cyclooctene or ethylene) are highly active catalysts for
alkyne hydrothiolation under mild conditions. A regioselectivity switch from linear to 1-substituted vinyl sulfides was observed
when mononuclear RhCl(IPr)(py)(η2-olefin) catalysts were used instead of dinuclear precursors. A complex interplay between electronic and steric effects exerted by IPr, pyridine, and hydride ligands accounts for the observed regioselectivity. Both IPr and pyridine ligands stabilize formation of square-pyramidal thiolate−hydride active species in which the encumbered and powerful electron-donor IPr ligand directs coordination of pyridine trans to it, consequently blocking access of the incoming alkyne in this position. Simultaneously, the higher trans director hydride ligand paves the way to a cis thiolate−alkyne disposition, favoring formation of 2,2-disubstituted metal−alkenyl species and subsequently the Markovnikov vinyl sulfides via alkenyl−hydride reductive elimination. DFT calculations support a plausible reaction pathway where migratory insertion of the alkyne into the rhodium−thiolate bond is the rate-determining step.