Benzocyclobutenone synthesis exploiting acylsilanes as photofunctional directing groups

Abstract

The visible-light irradiation of acylsilane tethered vinyl ketones promotes an intramolecular Stetter-type reaction via siloxycarbene intermediates. To exploit this unique mode of reactivity, we herein describe the innovative use of acylsilanes as photofunctional directing groups. First, an acylsilane directed ruthenium catalysed C-H olefination reaction was developed to generate benzoylsilanes bearing vinyl ketone functionality. Then, visible-light irradiation initiated the 1,4-conjugate addition of transient siloxycarbene intermediates with pendent vinyl ketones to afford unique benzocyclobutenone scaffolds primed for further synthetic elaboration.