Palladium-Catalyzed [3+2] Cycloaddition of Carbon Dioxide and Trimethylenemethane under Mild Conditions

Abstract

Carbon dioxide undergoes a Pd-catalyzed [3+2] cycloaddition with trimethylenemethane (TMM) under mild conditions (1 atm, 75 degrees C, 30 min) to produce a gamma-butyrolactone product in 63% yield, when the Pd-TMM complex is generated from 2-(acetoxymethyl)-3-(trimethylsilyl)propene. The reaction reported here is more rapid than the all-carbon [3+2] cycloaddition, and only the gamma-butyrolactone is produced in a competition experiment. With substituted substrates, the reaction is completely regioselective, producing the product derived from the kinetic Pd-TMM complex.

Recent Development in Palladium-Mediated Synthesis of Oxygen Heterocycles

“…A number of oxazolidine 88 and imidazolidine 89 derivatives were synthesized by [3+2] cycloaddition between oxiranes and aziridines with heterocumulenes. An extensive investigation on the palladium-catalyzed [3+2] cycloaddition reaction between 2-(acetoxymethyl)-3-(trimethylsilyl)propene 124a and carbon dioxide was reported by Greco et al 90 The reaction is presumed to proceed via the in situ generation of η 3 -Pd trimethylenemethane (TMM) complex-(A), the three atom partner, which underwent [3+2] cycloaddition with carbon dioxide to afford γ-butyro lacone 125 as the major product along with acetylated compound 126 (Scheme 40).…”

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

“…2.2.2). Recently, Greco and co-workers reported that these types of compounds can be used in isolated form as the precatalysts in the carboxylation of a formal methylenecyclopropane equivalent: 2-(acetoxymethyl)-3-(trimethylsilyl)propene [161]. Thus, similarly to Inoue's report, γ-butyrolactones were obtained via a [3 + 2] cycloaddition, but under much milder reaction conditions (1 bar, 75 C, 30 min).…”

Catalytic Domino Annulations through η3‐Allylpalladium Chemistry: A Never‐Ending Story

“…Besides investigations on the use of other dipolarophiles such as isocyanates or carbon dioxide, new reactivities with regard to Pd‐catalyzed [3+2]‐cycloaddition reactions have been recently highlighted.…”