biostudies-literatureNagamalla SNational Institute of General Medical SciencesNIGMS NIH HHS939-943https://www.ebi.ac.uk/biostudies/studies/S-EPMC8965746biostudies-literatureUnknown24(3)We present a new ring-opening reaction of epoxides by pendant silanols, catalyzed by either Ph₃C⁺BF₄^- or BINOL-phosphoric acid. Silanol epoxides derived from <i>trans</i>-allylic alcohols, <i>cis</i>-allylic alcohols, <i>trans</i>-homoallylic alcohols, and <i>cis</i>-homoallylic alcohols were all compatible and gave products from either <i>endo</i>- or <i>exo</i>-ring opening. With silanol epoxides derived from 4-alkenyl silanols, an unusual rearrangement to tetrahydrofuran products was observed. The utility of this methodology was demonstrated in a short preparation of protected d-arabitol.Organic lettersRing Opening of Epoxides by Pendant Silanols.PMC8965746R35 GM142499R35GM142499Sathyamoorthi SNagamalla SMague JTfalseRing Opening of Epoxides by Pendant Silanols.We present a new ring-opening reaction of epoxides by pendant silanols, catalyzed by either Ph₃C⁺BF₄^- or BINOL-phosphoric acid. Silanol epoxides derived from <i>trans</i>-allylic alcohols, <i>cis</i>-allylic alcohols, <i>trans</i>-homoallylic alcohols, and <i>cis</i>-homoallylic alcohols were all compatible and gave products from either <i>endo</i>- or <i>exo</i>-ring opening. With silanol epoxides derived from 4-alkenyl silanols, an unusual rearrangement to tetrahydrofuran products was observed. The utility of this methodology was demonstrated in a short preparation of protected d-arabitol.2022-01-01T00:00:00Z2022 Jan2025-04-04T19:10:02.183Z2025-04-04T19:10:02.183ZS-EPMC89657463504143710.1021/acs.orglett.1c04310