Acid‐Catalyzed Carbene Transfer from Diazo Compounds: Carbocation versus Carbene as Key Intermediate

An efficient mechanism for the acid‐catalyzed formal carbene transfer from diazo compounds to nucleophilic substrates is disclosed by DFT calculations. In sharp contrast to recent proposal via neutral carbene‐like intermediates, the new mechanism involves selective diazo C‐protonation to form cataly...

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Bibliographic Details
Published inEuropean journal of organic chemistry Vol. 2022; no. 17
Main Authors Qu, Zheng‐Wang, Zhu, Hui, Grimme, Stefan
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 06.05.2022
Subjects
Carbenes
Carbocations
Diazo compounds
Electrophilic substitution
Protonation
Reaction mechanisms
Substrates
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Summary:An efficient mechanism for the acid‐catalyzed formal carbene transfer from diazo compounds to nucleophilic substrates is disclosed by DFT calculations. In sharp contrast to recent proposal via neutral carbene‐like intermediates, the new mechanism involves selective diazo C‐protonation to form catalytic electrophilic carbocations, thus enabling a broad choice of metal‐free acid catalysts and nucleophilic substrates. An efficient and general mechanism of acid‐catalyzed formal carbene transfer from diazo compounds is disclosed by state‐of‐the‐art DFT calculations, suggesting electrophilic carbocations instead of neutral carbenes as the actual catalytic species.
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ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202200408