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. 2023 May 21;10(10):2556-2562.
doi: 10.1039/d3qo00427a. Epub 2023 Apr 24.

Dancing Silanols: Stereospecific Rearrangements of Silanol Epoxides into Silanoxy-Tetrahydrofurans and Silanoxy-Tetrahydropyrans

Harshit Joshi  1 , Annu Anna Thomas  1 , Joel T Mague  2 , Shyam Sathyamoorthi  1
Affiliations

Dancing Silanols: Stereospecific Rearrangements of Silanol Epoxides into Silanoxy-Tetrahydrofurans and Silanoxy-Tetrahydropyrans

Harshit Joshi et al. Org Chem Front. .

Abstract

We have developed highly stereospecific rearrangements of silanol epoxides into 1'-silanoxy-tetrahydrofurans and 1'-silanoxy-tetrahydropyrans. Upon treatment with Ph3CBF4 and NaHCO3 in CH2Cl2, di-substituted trans-epoxide silanols rearrange into products with an erythro configuration; di-substituted cis-epoxide silanols give products with a threo configuration. We have used these reactions as key steps in the syntheses of (±)-solerone and (±)-muricatacin.

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Conflict of interest statement

Conflicts of interest There are no conflicts to declare.

Figures

Scheme 1
Scheme 1
Current approaches to 1'-hydroxy-tetrahydrofurans contrasted with our own.
Scheme 2
Scheme 2. Substrate Scope (trans epoxides).
aSubstrate number, Product number. Note: All compounds shown are racemic, and relative stereochemistry is depicted.
Scheme 3
Scheme 3. Substrate Scope (cis epoxides).
aSubstrate number, Product number. Note: All compounds shown are racemic, and relative stereochemistry is depicted.
Scheme 4
Scheme 4
Scale-up reaction.
Scheme 5
Scheme 5. Preparation of Silanoxy-Tetrahydropyrans.
aSubstrate number, Product number. Note: All compounds shown are racemic, and relative stereochemistry is depicted.
Scheme 6
Scheme 6
Probe substrates help delineate a possible mechanism of rearrangement.
Scheme 7
Scheme 7
Application of the rearrangement reaction for the syntheses of (A) (±)-solerone and (B) (±)-muricatacin.
See this image and copyright information in PMC

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