Unknown

Dataset Information

0

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···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.

SUBMITTER: Lee HJ 

PROVIDER: S-EPMC10955696 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

altmetric image

Publications

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

Lee Hye Jin HJ   Jang Seohyeon S   Kim Tae Yong TY   Han Jeong Woo JW   Nam Inho I   Baek Jayeon J   Kim Yong Jin YJ  

ACS omega 20240311 11


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]<sup>δ-</sup>[DMAP(CO)OR]<sup>δ+</sup> (IV) via nucleophilic substitution of DMAP at the carbonyl group of DMAP···HSe(CO)OR is the most energetically favorable. DM  ...[more]

Similar Datasets

| S-EPMC5347984 | biostudies-literature
| S-EPMC10098644 | biostudies-literature
| S-EPMC3423973 | biostudies-literature
| S-EPMC11835170 | biostudies-literature
| S-EPMC5753116 | biostudies-literature
| S-EPMC9041312 | biostudies-literature
| S-EPMC7898928 | biostudies-literature
| S-EPMC10806816 | biostudies-literature
| S-EPMC4156261 | biostudies-literature
| S-EPMC5676093 | biostudies-literature