Abstract:

The pivotal role of arylsilanes as synthetic intermediates together with their use in medicinal chemistry and material science has attracted the attention and interest of the synthetic community. The synthesis of arylsilanes is typically accomplished via the reaction of stoichiometric and highly reactive organolithium or Grignard reagents with activated silicon sources (path a). Alternatively, aryl halides can be used as coupling partners (path b); however, the need for organic halides and the use of strongly reducing trialkylsilanes still constitute serious drawbacks when preparing backbones with sensitive functional groups. In recent years, the utilization of C-O electrophiles as coupling partners has received a great deal of attention due to their lack of toxicity and the readily availability of phenol as compared to commonly employed aryl halides as counterparts. While formidable advances have been realized in this area of expertise, to the best of our knowledge, the development of a catalytic C-Si bondforming event using simple and inert C-O bonds has no precedents in the literature. Herein, we report the success of this approach via Ni-catalyzed silylation of unactivated aryl esters via C-O bond-activation (path c).