title: Reduction of cyclic group 6 Fischer carbene complexes: a case of exquisite regioselectivity.
abstract: The reduction of alpha,beta-unsaturated cyclic group 6 metal-carbene complexes strongly depends on the electronic profile of the groups attached both to the carbene and the beta-carbon and occurs with exquisite regioselectivity. Thus, for complexes 8 the reduction does not take place at the carbene carbon but exclusively at the gamma-carbonyl group. The resulting alkoxide 20 evolves to a tricyclic epoxide structure 21, which precludes additional hydride transfers. Complex 9 experiences the exclusive 1,4-reduction because of the imino character of the beta-carbon (due to the participation of the aromatic resonance form 22). In contrast, monocyclic carbene complexes 10 behave as their acyclic congeners and experience 1,2-hydride addition followed by the 1,3-migration of the metal center. In this case, the participation of eta(3)-Cr(CO)(5) species 31 allows us to understand the labeling pattern found in the final products.
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040-Madrid, Spain.
authors.forename: Pedro
authors.initials: P
authors.lastname: Ramírez-López
authors.forename: Mar
authors.initials: M
authors.lastname: Gómez-Gallego
authors.forename: María José
authors.initials: MJ
authors.lastname: Mancheño
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Sierra
authors.forename: Montse
authors.initials: M
authors.lastname: Bilurbina
authors.forename: Susagna
authors.initials: S
authors.lastname: Ricart