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Rhodium(I)-Catalyzed CO-Gas-Free Arylative Dual-Carbonylation of Alkynes with Arylboronic Acids via the Formyl C–H Activation of Formaldehyde

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The rhodium(I)-catalyzed reaction of alkynes with aryl­boronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce γ-butenolide derivatives. The simultaneous loading of phosphine-ligated and phosphine-free… Click to show full abstract

The rhodium(I)-catalyzed reaction of alkynes with aryl­boronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce γ-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 γ-butenolides via the dual-incorporation of the carbonyl unit.

Keywords: gas free; rhodium catalyzed; free arylative; arylative dual; carbonylation; rhodium

Journal Title: Synthesis
Year Published: 2021

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