Acid‐Catalyzed Carbene Transfer from Diazo Compounds: Carbocation versus Carbene as Key Intermediate. Issue 17 (2nd May 2022)

• Record Type: Journal Article
• Authors: Qu, Zheng‐Wang; Zhu, Hui; Grimme, Stefan
• Is Part Of: European journal of organic chemistry. Volume 2022:Issue 17(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-02
• Subjects: Carbocations -- Diazo compounds -- Electrophilic substitution -- Protonation -- Reaction mechanisms; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202200408
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: 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. Abstract : 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.