CS₂/CO₂ Utilization Using Mukaiyama Reagent as a (Thio)carbonylating Promoter: A Proof-of-Concept Study

We report on the reaction of ethylene-terminated heteroatoms (C₂X; X = N, O, and S) with CS₂/CO₂ 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., ¹H/¹³C nuclear magnetic resonance (NMR) and ex situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy methods verified the reaction of CS₂/CO₂ 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.