Unveiling the Role of DMAP for the Se-Catalyzed Oxidative Carbonylation of Alcohols: A Mechanism Study

Abstract

Considering the remarkable catalytic activity (160 times higher) of Se/DMAP for the oxidative carbonylation of alcohols, unveiling the role of DMAP in catalysis is highly required. We investigated DFT calculations, and the proposed intermediates were verified with in situ ATR-FTIR analysis. DFT showed that the formation of [DMAP<middle dot><middle dot><middle dot>HSe](delta-)[DMAP(CO)OR](delta+) (IV) via nucleophilic substitution of DMAP at the carbonyl group of DMAP<middle dot><middle dot><middle dot>HSe(CO)OR is the most energetically favorable. DMAP acts as both a nucleophile and a hydrogen bond acceptor, which is responsible for its remarkable activity.