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Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity

The Simmons–Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal–carbon multiple bonds. Herein, we describe this type of reaction...

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Detalles Bibliográficos
Autores principales: Huang, Fanping, Zheng, Xuejuan, Lin, Xinlei, Ding, Linting, Zhuo, Qingde, Wen, Ting Bin, Zhang, Hong, Xia, Haiping
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162146/
https://www.ncbi.nlm.nih.gov/pubmed/34094279
http://dx.doi.org/10.1039/d0sc03215h
Descripción
Sumario:The Simmons–Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal–carbon multiple bonds. Herein, we describe this type of reaction and the construction of three-membered rings has now been applied in organometallic systems by combining classical zinc carbenoid reagents with a range of structurally and electronically diverse metal carbynes. A variety of metallacyclopropene derivatives prepared in this way represent rare examples with σ-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations.