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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

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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]

PMID: 38524452

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