Organic Chemistry

A Rearrangement of Allylic Silanols

Authors

Abstract

We show that 1M aq. 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.


Content

Thumbnail image of Manuscript-fs-1-17.pdf

Supplementary material

Thumbnail image of q20l.txt
q20l
Thumbnail image of Supporting Information-fs-1-17.pdf
Supporting Information-fs-1-17