Our success with the range of substrates shown in Schemes 2 and 3 prompted us to apply this rearrangement reaction as a key step in the syntheses of 7A) and (±)-muricatacin (Scheme 7B). Solerone is a natural product which contributes to the aroma of certain wines and has been demonstrated to be a key intermediate in the syntheses of larger chromanones. Conversion of silanoxy-tetrahydrofuran 2 into lactone 79 proceeded oxidation with Treatment with HF•pyridine removed the silanol group, and DMP oxidation of the resulting alcohol gave solerone in three steps from 2 (Scheme 7A). A similar sequence, commencing with silanoxy-tetrahydrofuran 46, allowed for a concise preparation of (±)-muricatacin (Scheme 7B). We were particularly excited by this result, as muricatacin is a known anti-tumor cytotoxin and is a demonstrated synthetic intermediate for acetogenin natural products. In summary, we have developed highly stereospecific rearrangements of silanol epoxides into 1'-silanoxytetrahydrofurans and 1'-silanoxy-tetrahydropyrans. Upon treatment with Ph3CBF4 and NaHCO3 in CH2Cl2, trans-disubstituted silanol epoxides rearrange into products with an erythro configuration; cis-di-substituted epoxides give products with a threo configuration. To our knowledge, this transformation has little literature precedent. Control experiments show that the rearrangement reaction likely proceeds by nucleophilic attack of the proximal silanol oxygen onto the epoxide followed by an intramolecular silyl transfer. We have used these reactions as key steps in the syntheses of (±)-solerone and (±)-muricatacin. Rearrangements have captivated organic chemists for more than a century, and we are pleased to add examples to this storied class of transformations.