Benzocyclobutenone synthesis exploiting acylsilanes as photofunctional directing groups
Rowan L Pilkington1, Hannah J Ross1, Liselle Atkin1
1Medicinal Chemistry Theme, Monash Institute of Pharmaceutical Sciences, Monash University Parkville VIC 3052 Australia daniel.priebbenow@monash.edu.
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.
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