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Updated: Jun 4, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
An Experimental and Computational Investigation into the Allylboration/Defluorinative Semipinacol Rearrangement
Ty Dudas1, Austin Pounder1, Isabella M Umeris1
1Canadian Centre for Research in Advanced Fluorine Technologies and Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, AB T1K 3M4, Canada.
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.
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