DFT mechanistic insight into the modular strategy involved in the palladium-catalyzed synthesis of cyclopentenones from α,β-unsaturated acid chlorides and alkynes

ZHONG Liang; ZHAO Ruihua; WANG Zhixiang

doi:10.7523/j.ucas.2021.0046

Journal of University of Chinese Academy of Sciences >

2022 , Vol. 39 >Issue 2: 145 - 153

DOI: https://doi.org/10.7523/j.ucas.2021.0046

Innovation Article

DFT mechanistic insight into the modular strategy involved in the palladium-catalyzed synthesis of cyclopentenones from α,β-unsaturated acid chlorides and alkynes

ZHONG Liang ,
ZHAO Ruihua ,
WANG Zhixiang

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School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China

Received date: 2021-04-19

Revised date: 2021-05-19

Online published: 2021-05-19

Supported by

Supported by the National Natural Science Foundation of China (21773240)

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Abstract

Cyclopentenones are important synthetic building blocks and as motifs appear in bioactive molecules and natural products. We applied density functional theory (DFT) calculations to gain insight into the modular strategy involved in the palladium-catalyzed synthesis of cyclopentenone from α,β-unsaturated acid chlorides and alkynes in the presence of hydrosilane. The study unveils that the transformation proceeds via the sequence:the disassembly of α,β-unsaturated acid chloride into vinyl, carbonyl, and Cl fragments with the palladium catalyst; carbon monoxide release; coupling of alkyne with vinyl group; carbon monoxide re-coordination and migratory insertion to form another C-C bond with alkyne, ring-closure via C=C bond insertion, transmetalation with hydrosilane, C, H-reductive elimination to release the product. Different from the mechanism proposed by the experimentalists, the CO group is involved in the reaction via separate liberation and re-coordination in the solvent cage, rather than persistent coordination with palladium. The transmetalation for H/Cl exchange takes place at the late stage and is a bottleneck of the transformation, instead of at early disassembly stage.

Key words： cyclopentenone synthesis; modular strategy; carbon monoxide surrogates; palladium catalysis; DFT calculation

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ZHONG Liang , ZHAO Ruihua , WANG Zhixiang . DFT mechanistic insight into the modular strategy involved in the palladium-catalyzed synthesis of cyclopentenones from α,β-unsaturated acid chlorides and alkynes[J]. Journal of University of Chinese Academy of Sciences, 2022 , 39(2) : 145 -153 . DOI: 10.7523/j.ucas.2021.0046

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