Synthesis of unstrained Criegee intermediates: inverse α-effect and other protective stereoelectronic forces can stop Baeyer-Villiger rearrangement of γ-hydroperoxy-γ-peroxylactones.

ABSTRACT: How far can we push the limits in removing stereoelectronic protection from an unstable intermediate? We address this question by exploring the interplay between the primary and secondary stereoelectronic effects in the Baeyer-Villiger (BV) rearrangement by experimental and computational studies of γ-OR-substituted γ-peroxylactones, the previously elusive non-strained Criegee intermediates (CI). These new cyclic peroxides were synthesized by the peroxidation of γ-ketoesters followed by in situ cyclization using a BF₃·Et₂O/H₂O₂ system. Although the primary effect (alignment of the migrating C-R_m bond with the breaking O-O bond) is active in the 6-membered ring, weakening of the secondary effect (donation from the OR lone p

SUBMITTER: Vil' VA 

PROVIDER: S-EPMC8159355 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature