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...

Descripción completa

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
_version_ 1783720766891622400
author Dhokale, Ranjeet A.
Seidl, Frederick J.
Sathyamoorthi, Shyam
author_facet Dhokale, Ranjeet A.
Seidl, Frederick J.
Sathyamoorthi, Shyam
author_sort Dhokale, Ranjeet A.
collection PubMed
description 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.
format Online
Article
Text
id pubmed-8270268
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-82702682021-07-10 A Formal Rearrangement of Allylic Silanols Dhokale, Ranjeet A. Seidl, Frederick J. Sathyamoorthi, Shyam Molecules Article 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. MDPI 2021-06-23 /pmc/articles/PMC8270268/ /pubmed/34201779 http://dx.doi.org/10.3390/molecules26133829 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Dhokale, Ranjeet A.
Seidl, Frederick J.
Sathyamoorthi, Shyam
A Formal Rearrangement of Allylic Silanols
title A Formal Rearrangement of Allylic Silanols
title_full A Formal Rearrangement of Allylic Silanols
title_fullStr A Formal Rearrangement of Allylic Silanols
title_full_unstemmed A Formal Rearrangement of Allylic Silanols
title_short A Formal Rearrangement of Allylic Silanols
title_sort formal rearrangement of allylic silanols
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8270268/
https://www.ncbi.nlm.nih.gov/pubmed/34201779
http://dx.doi.org/10.3390/molecules26133829
work_keys_str_mv AT dhokaleranjeeta aformalrearrangementofallylicsilanols
AT seidlfrederickj aformalrearrangementofallylicsilanols
AT sathyamoorthishyam aformalrearrangementofallylicsilanols
AT dhokaleranjeeta formalrearrangementofallylicsilanols
AT seidlfrederickj formalrearrangementofallylicsilanols
AT sathyamoorthishyam formalrearrangementofallylicsilanols

Ejemplares similares