Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

Alkenyl‐to‐allyl 1,4‐rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C−H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1,3‐enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur‐alkene ligand.