Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids

[Image: see text] We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolved through a cyclopropanation process providing access to densely functionalized cyclopr...

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Detalles Bibliográficos
Autores principales: Palomo, Eric, Sharma, Akhilesh K., Wang, Zhaofeng, Jiang, Liyin, Maseras, Feliu, Suero, Marcos G.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9999426/
https://www.ncbi.nlm.nih.gov/pubmed/36812070
http://dx.doi.org/10.1021/jacs.3c00012
Descripción
Sumario:[Image: see text] We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed the analysis of the properties of Rh(II)-carbynoids and acyloxy Rh(II)-carbenes as well as the characterization of the mechanism.

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