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A Formal Rearrangement of Allylic Silanols.

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.

SUBMITTER: Dhokale RA

PROVIDER: S-EPMC8270268 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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A Formal Rearrangement of Allylic Silanols.

Dhokale Ranjeet A RA Seidl Frederick J FJ Sathyamoorthi Shyam S

Molecules (Basel, Switzerland) 20210623 13

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 sugge ...[more]

PMID: 34201779

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