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

## TL;DR

This study reveals how DMAP enhances the catalytic activity of selenium in converting alcohols through oxidative carbonylation.

## Contribution

The paper identifies the specific role of DMAP as both a nucleophile and hydrogen bond acceptor in the catalytic mechanism.

## Key findings

- DFT calculations show that DMAP forms an energetically favorable intermediate via nucleophilic substitution.
- In situ ATR-FTIR analysis confirms the proposed intermediates in the reaction pathway.
- DMAP's dual role explains the high catalytic efficiency of the Se/DMAP system.

## 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···HSe]δ−[DMAP(CO)OR]δ+ (IV) via nucleophilic
substitution of DMAP at the carbonyl group of DMAP···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.