DFT calculations reveal the origin of controllable synthesis of β-boronyl carbonyl compounds from Cu/Pd-cocatalyzed four-component borocarbonylation of vinylarenes

Abstract

This paper shows a DFT-based comparative mechanistic study on the Cu/Pd-cocatalyzed four-component borocarbonylative reactions between vinylarenes, aryl halides/triflates, bis(pinacolato)diboron (B2pin2), and CO to rationalize the experimental observation that aryl iodides...

Transforming carbon dioxide and carbon monoxide into value-added products: boracarboxylation and boracarbonylation

“…The substrate scope with a wide range of alkenes spanning from aryl rings having electrondonating and -withdrawing substituents at the para/meta positions, also including heterocycles and esters, was explored to afford the corresponding β-boryl ketones in Later, theoretical studies were carried out to show the difference in the reactivity of cooperative Cu/Pd-catalyzed four-component borocarbonylation reaction. 93 The study illustrates that the reactivity difference is due to different formation rates of the reactive intermediates in the Cucatalytic cycle compared to those in the Pd-catalytic cycle, originating from different starting materials (aryl halides/ triflates). According to the mechanism, Cu and Pd catalysts independently activate vinylarenes and arylhalides (or triflates), yielding vinyl alkoxide-and alkyl copper derivatives in the Cu-cycle as well as acyl and aryl palladium derivatives in the Pd cycle.…”