CS(2)/CO(2) Utilization Using Mukaiyama Reagent as a (Thio)carbonylating Promoter: A Proof-of-Concept Study

[Image: see text] We report on the reaction of ethylene-terminated heteroatoms (C(2)X; X = N, O, and S) with CS(2)/CO(2) using Mukaiyama reagent (2-chloro-1-methylpyridinium iodide, CMPI) as a promoter for the preparation of imidazolidin-2-one, oxazolidin-2-one, 1,3-dioxolan-2-one, 1,3-dithiolan-2-one, and their thione counterparts at ambient temperature and pressure. Spectroscopic measurements, viz., (1)H/(13)C nuclear magnetic resonance (NMR) and ex situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy methods verified the reaction of CS(2)/CO(2) with the ethylene-based substrates and subsequently the formation of cyclic products. The experimental data indicated the formation of the enol-form of imidazolidin-2-one and oxazolidin-2-one, while the keto-form was obtained for their thione correspondents. Furthermore, density functional theory calculations revealed the stability of the keto- over the enol-form for all reactions and pointed out the solvent effect in stabilizing the latter.