An Experimental and Computational Investigation into the Allylboration/Defluorinative Semipinacol Rearrangement Cascade Reaction

The Journal of Organic Chemistry 2026 Open access

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Authors: Ty Dudas, Austin Pounder, Isabella M. Umeris, Taylor Semeniuk, Stacey D. Wetmore, Jean‐Denys Hamel
DOI: 10.1021/acs.joc.5c03050
Cited by: 1
References: 36

Abstract

Allylboration reactions using (3-fluoroallyl)boronates enable concurrent C-C bond formation and C-F bond activation through a cascade process. The resulting borate adduct promotes a defluorinative semipinacol rearrangement, generating α-functionalized carbonyl products through a coupled C-F cleavage/1,2-migration sequence. The transformation proceeds with high selectivity for aryl migration and tolerates a range of carbonyl substrates. Computational analysis clarifies the electronic factors governing the experimentally observed migratory aptitude trends, providing mechanistic insight into this distinct mode of defluorination-driven skeletal reorganization.

Fields of Study & Subjects

Mesoporous Materials and Catalysis Cancer Treatment and Pharmacology

Publication details

Journal / source
The Journal of Organic Chemistry
Publisher
American Chemical Society (ACS)
Volume
91
Issue
23
Pages
7730–7737
Publication date
3 June 2026
Language
EN