NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization

Zwitterionic adducts of N-heterocyclic carbene and carbodiimide (NHC-CDI) are an emerging class of organic compounds with promising properties for applications in various fields. Herein, we report the use of the ICyCDI(p-Tol) betaine adduct (1a) and its cationic derivatives 2a and 3a as catalyst precursors for the dichloromethane valorization via transformation into high added value products CH₂Z₂ (Z = OR, SR or NR₂). This process implies selective chloride substitution of dichloromethane by a range of nucleophiles Na⁺Z^- (preformed or generated in situ from HZ and an inorganic base) to yield formaldehyde-derived acetals, dithioacetals, or aminals with full selectivity. The reactions are conducted in a multigram-scale under very mild conditions, using dichloromethane both as a reagent and solvent, and very low catalyst loading (0.01 mol %). The CH₂Z₂ derivatives were isolated in quantitative yields after filtration and evaporation, which facilitates recycling the dichloromethane excess. Mechanistic studies for the synthesis of methylal CH₂(OMe)₂ rule out organocatalysis as being responsible for the CH₂ transfer, and a phase-transfer catalysis mechanism is proposed instead. Furthermore, we observed that 1a and 2a react with NaOMe to form unusual isoureate ethers, which are the actual phase-transfer catalysts, with a strong preference for sodium over other alkali metal nucleophiles.