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The enantioselective synthesis of densely functionalized polycarbocycles by the rhodium(i)-catalyzed reaction of arylboronic acids with 1,3-diketones is described. The key step in these desymmetrizing domino addition-cyclization reactions is an alkenyl-to-aryl 1,4-Rh(i) migration, which enables arylboronic acids to function effectively as 1,2-dimetalloarene surrogates.

Catalytic enantioselective arylative cyclizations of alkynyl 1,3-diketones by 1,4-rhodium(i) migration