Rhodium-catalyzed sequential intermolecular hydroacylation and deconjugative isomerization toward diversified diketones

A rhodium-catalyzed tandem intermolecular hydroacylation of terminal alkyne-substituted secondary alcohols with chelating aldehydes and deconjugative isomerization of the resulting α,β-unsaturated ketones for the preparation of synthetically valuable 1,4-diketones is developed. Of note, the completely atom-economical protocol can be extended to the alkynyl alcohols with appropriate carbon chain length, from which 1,5-diketone and 1,6-diketone were obtained involving the short-range deconjugative isomerization. Given its robustness, broad substrate scope, and excellent regioselectivity, this approach provides a promising platform for the synthesis of diverse diketones.