A Formal Rearrangement of Allylic Silanols

We show that 1M aqueous HCl/THF or NaBH(4)/DMF allows for demercurative ring-opening of cyclic organomercurial synthons into secondary silanol products bearing terminal alkenes. We had previously demonstrated that primary allylic silanols are readily transformed into cyclic organomercurials using Hg...

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Detalles Bibliográficos
Autores principales: Dhokale, Ranjeet A., Seidl, Frederick J., Sathyamoorthi, Shyam
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8270268/
https://www.ncbi.nlm.nih.gov/pubmed/34201779
http://dx.doi.org/10.3390/molecules26133829
Descripción
Sumario:We show that 1M aqueous HCl/THF or NaBH(4)/DMF allows for demercurative ring-opening of cyclic organomercurial synthons into secondary silanol products bearing terminal alkenes. We had previously demonstrated that primary allylic silanols are readily transformed into cyclic organomercurials using Hg(OTf)(2)/NaHCO(3) in THF. Overall, this amounts to a facile two-step protocol for the rearrangement of primary allylic silanol substrates. Computational investigations suggest that this rearrangement is under thermodynamic control and that the di-tert-butylsilanol protecting group is essential for product selectivity.

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