Stille Cross-Coupling Reactions of Alkenylstannanes with Alkenyl Iodides Mediated by Copper(I) Thiophene-2-carboxylate: A Density Functional Study
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Abstract
The detailed reaction mechanism for the Stille cross-coupling reaction of vinylstannane with vinyl iodide mediated by copper(I) thiophene-2-carboxylate (CuTC) was studied with the aid of density functional theory (DFT) calculations. The results of the DFT calculations show that the reaction mechanism involves two major steps: (1) the transmetalation between (NMP)CuTC (NMP = N-methylpyrrolidone, a solvent molecule) and CH2═CHSnMe3 to give the organocopper intermediate (NMP)Cu-CH═CH2 and (2) a one-step process involving both oxidative addition of CH2═CHI to (NMP)Cu-CH═CH2 and reductive elimination of the coupling product CH2═CH−CH═CH2. We found that the overall barrier involves the effect of both steps. In this paper, we also examined the role of the thiophene-2-carboxylate ligand in the reaction and discussed the possibility of a catalytic version of the reaction.
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