Rhodium(I)-catalyzed CO-gas-free arylative dual-carbonylation of alkynes with arylboronic acids via the formyl C-H activation of formaldehyde

Abstract

The rhodium(I)-catalyzed reaction of alkynes with aryl-boronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce gamma-butenolide derivatives. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis. The former complex catalyzes the abstraction of a carbonyl moiety from formaldehyde through the activation of its formyl C-H bond (decarbonylation) and the latter catalyzes the subsequent dual-incorporation of the resulting carbonyl unit (carbonylation). The use of larger amounts of the phosphine-ligated rhodium(I) complex generates more carbonyl units, leading to the formation gamma-butenolides via the dual-incorporation of the carbonyl unit.