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Cp*RuCl-Vinyl Carbenes: Two Faces and the Bifunctional Role in Catalytic Processes
Authors:Dr. Damián Padín  Prof. Jesús A. Varela  Prof. Carlos Saá
Affiliation:Centro Singular de Investigación en Química Biolóxica e, Materiais Moleculares (CiQUS), Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Abstract:Ruthenium vinyl carbenes derived from Cp/Cp*RuCl-based complexes (Cp=cyclopentadiene, Cp*=1,2,3,4,5-pentamethylcyclopentadiene) have been routinely invoked as key intermediates in tandem reactions involving a carbene/alkyne metathesis (CAM). A priori, these intermediates resemble the Grubbs-type family of catalysts, but they exhibit a completely different reactivity pattern that few, if any, other catalytic system can reproduce so far. The reactivity of these species with α-unsubstituted and α-substituted alkynals showcases the peculiarities of these intermediates. Although Z-vinyl dihydrooxazines are preferentially obtained with the former, Z-vinyl epoxypyrrolidines are obtained with the latter. A combination of spectroscopic and computational data now prove that a η3-coordination mode of the ruthenium vinyl carbene and the presence of a Lewis basic chloride ligand give rise to two markedly different stereoelectronic faces, which are responsible for the unconventional reactivity of these species.
Keywords:carbenes  cycloadditions  metathesis  ruthenium  ylides
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