Access to allyl-<i>gem</i>-difluorides <i>via</i> allylation and Cope rearrangement.

ABSTRACT: Fluorinated molecules play crucial roles in medicinal and materials chemistry, as the presence of fluorine profoundly alters molecular electronics and reactivity. Among them, allyl gem-difluorides have attracted growing attention as versatile synthetic intermediates, but their selective construction remains challenging. Here, we disclose an efficient strategy for synthesizing allyl gem-difluorides bearing (E)-vinyl boronic esters through a LiOtBu-mediated deborylative allylation/Cope rearrangement sequence of 3-boryl-1,1-difluoro allylboronic ester with allyl bromides. Four competing pathways (α-S_N2, α-S_N2', γ-S_N2, and γ-S_N2') were identified: α-addition generates intermediates that undergo Cope rearrangement, while γ-

SUBMITTER: Kim H 

PROVIDER: S-EPMC12696483 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature