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.
A novel multicomponent coupling reaction involving the iridium-catalyzed 1,5-difunctionalization of 1,3-enynes with arylboronic acids and triazinanes is described.
A chiral rhodium complex catalyzes the highly enantioselective coupling of arylboronic acids, 1,3‐enynes, and imines to give homoallylic sulfamates. The key step is the generation of allylrhodium(I) species by alkenyl‐to‐allyl 1,4‐rhodium(I) migration.
The enantioselective synthesis of densely functionalized polycarbocycles by the rhodium(i)-catalyzed reaction of arylboronic acids with alkynyl 1,3-diketones is described. The key step in these reactions is an alkenyl-to-aryl 1,4-Rh(i) migration..
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