Preparation of Dienyl Boronates by Tandem Ene-Yne Metathesis/Dienyl Isomerization: Ready Access to Diene Building Blocks for the Synthesis of Polyenes.

The ene-yne metathesis of alkenyl boronates with terminal alkynes is reported. These challenging metatheses were accomplished using a Grubbs catalyst bearing the cyclic alkyl amino carbene (CAAC) ligand, whereas -heterocyclic carbene (NHC) derived catalysts gave lower yields. Subsequent dienyl isomerization via a cobalt-catalyzed hydrogen atom transfer (HAT) furnished the more substituted dienyl boronate with high / ratios. Finally, the resulting dienyl boronate products were successfully used in Suzuki-Miyaura cross-coupling reactions and in a Diels-Alder cycloaddition.