title: Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion.
abstract: The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units :CHCO(2)Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N(2)C(Ph)CO(2)Et displays similar reactivity to that of EDA, whereas other N(2)C(R)CO(2)Et (R = Me, CO(2)Et) gave lower conversions.
authors.affiliation: Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible, Universidad de Huelva, Campus de El Carmen, 21007-Huelva, Spain.
authors.forename: M José
authors.initials: MJ
authors.lastname: Iglesias
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Nicasio
authors.forename: Ana
authors.initials: A
authors.lastname: Caballero
authors.forename: Pedro J
authors.initials: PJ
authors.lastname: Pérez