Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions

Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride ion with GaCl3. The aryl carbenes react with PPh3 and alkenes to giv...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-03, Vol.58 (12), p.3957-3961
Main Authors: García‐Morales, Cristina, Pei, Xiao‐Li, Sarria Toro, Juan M., Echavarren, Antonio M.
Format: Article
Language:English
Subjects:
Alkenes
Aromatic compounds
Carbenes
carbenoids
Communication
Communications
Cyclohexane
density-functional calculations
Dimerization
Gallium chloride
Gold
Insertion
Ligands
Nucleophiles
Organic compounds
Oxidation
Pyridines
Shielding
structure elucidation
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Summary:Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride ion with GaCl3. The aryl carbenes react with PPh3 and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N‐oxide and intermolecular C−H insertion to cyclohexane have also been observed. In the absence of nucleophiles, a bimolecular reaction, similar to that observed for other metal carbenes, leads to a symmetrical alkene. Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride ion with GaCl3, and they were spectroscopically characterized. The aryl carbenes react with PPh3 and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N‐oxide and intermolecular C−H insertion to cyclohexane have also been observed.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201814577