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Published on: August 16, 2018
A Formal Rearrangement of Allylic Silanols
Ranjeet A Dhokale1, Frederick J Seidl2, Shyam Sathyamoorthi1
1Department of Medicinal Chemistry, University of Kansas, Lawrence, KS 66047, USA.
Abstract:
We 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.
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