Dhokale, Ranjeet A.Seidl, Frederick J.Sathyamoorthi, Shyam2021-12-082021-12-082021-06-23Dhokale, R.A.; Seidl, F.J.; Sathyamoorthi, S. A Formal Rearrangement of Allylic Silanols. Molecules 2021, 26, 3829. https://doi.org/10.3390/molecules26133829https://hdl.handle.net/1808/32274We show that 1M aqueous HCl/THF or NaBH4/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/NaHCO3 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.© 2021 by the authors. 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.http://creativecommons.org/licenses/by/4.0/RearrangementOrganic synthesisOrganic methodologyArticle10.3390/molecules26133829https://orcid.org/ 0000-0002-3587-0191https://orcid.org/ 0000-0001-9327-4753https://orcid.org/ 0000-0003-4705-7349PMC8270268openAccess