A Formal Rearrangement of Allylic Silanols
Ranjeet A. Dhokale, Frederick J. Seidl, Shyam Sathyamoorthi
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.
Topics & Concepts
Allylic rearrangementSynthonSilanolChemistrySelectivityRing (chemistry)Medicinal chemistryCombinatorial chemistryStereochemistryOrganic chemistryCatalysisChemical Synthesis and ReactionsOrganoboron and organosilicon chemistrySynthetic Organic Chemistry Methods