Assembly of Complex 1,4‐Cycloheptadienes by (4+3) Cycloaddition of Rhodium(II) and Gold(I) Non‐Acceptor Carbenes

The formal (4+3) cycloaddition of 1,3‐dienes with Rh(II) and Au(I) non‐acceptor vinyl carbenes, generated from vinylcycloheptatrienes or alkoxyenynes, respectively, leads to 1,4‐cycloheptadienes featuring complex and diverse substitution patterns, including natural dyctiopterene C′ and a hydroxylate...

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Detalles Bibliográficos
Autores principales: Armengol‐Relats, Helena, Mato, Mauro, Echavarren, Antonio M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Research Articles
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7894532/
https://www.ncbi.nlm.nih.gov/pubmed/33078893
http://dx.doi.org/10.1002/anie.202012092
Descripción
Sumario:The formal (4+3) cycloaddition of 1,3‐dienes with Rh(II) and Au(I) non‐acceptor vinyl carbenes, generated from vinylcycloheptatrienes or alkoxyenynes, respectively, leads to 1,4‐cycloheptadienes featuring complex and diverse substitution patterns, including natural dyctiopterene C′ and a hydroxylated derivative of carota‐1,4‐diene. A complete mechanistic picture is presented, in which Au(I) and Rh(II) non‐acceptor vinyl carbenes were shown to undergo a vinylcyclopropanation/Cope rearrangement or a direct (4+3) cycloaddition that takes place in a non‐concerted manner.

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