Palladium catalyzed arylation reactions of meta photocycloadducts

We describe the first application of a Heck arylation reaction being performed on a meta photocycloadduct. The resulting arylation/fragmentation process leads to the formation of a bridged bicyclic ketone and constitutes a dramatic increase in molecular complexity after just two synthetic operations

Palladium-mediated fragmentation of meta photocycloadducts using carbon based electrophiles: Part 1

Substituted benzene derived meta photocycloadducts have been shown to undergo a fragmentation/arylation reaction under Heck reaction conditions to give bridged bicyclo[3.2.1] compounds in a highly atom-efficient manner. When an anisole derived meta photocycloadduct is used, a bridgehead ketone is generated. However, if an alkylbenzene derived meta photocycloadduct is used, a bridgehead alkene is formed. This strategy has been used to create novel enol ether and transient allyl silane compounds