Theoretical Study on the Formation of 2‑Pyrone Derivatives from the Reaction of Alkynes with Carbon Dioxide in the Presence of Nickel Catalyst

The formation of 2-pyrone derivatives by the reaction of CO2 with a model internal alkyne, 2-butyne, in the presence of (cod)2Ni and a bisphosphine ligand (dppb), was studied using the M06/6-311G­(d,p) density functional theory method, which revealed that the reaction takes place in three stages. The first stage is the formation of the 2-butyne complex intermediate (dppb)­Ni­(η2-MeCCMe). There are several pathways for the formation of 2-pyrone complexes from it, and the more favorable two pathways were found among them. In the second stage, the coupling of (dppb)­Ni­(η2-MeCCMe) with 2-butyne or CO2 produces nickelacyclopentadiene or oxanickelacyclopentenone with the Ni–O bond, respectively. In the third stage, the reaction of CO2 with nickelacyclopentadiene or that of 2-butyne with oxanickelacyclopentenone produces 2-pyrone Ni complexes. The rate-limiting step is the second, in which nickelacyclopentadiene or oxanickelacyclopentenone is formed. The formation of oxanickelacyclopentenone with the Ni–O bond is kinetically more favorable, while the formation of nickelacyclopentadiene is thermodynamically more favorable. Thus, depending on the experimental conditions, the two pathways are in competition. This supports the mechanisms suggested by Inoue et al. and Hoberg et al., and we discuss the factors that make these mechanisms more favorable.