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Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>‐Initiated Grob Fragmentation

Kaixue Xie, Martin Oestreich

2022Angewandte Chemie International Edition21 citationsDOIOpen Access PDF

Abstract

Abstract Readily available cyclohexa‐2,5‐dien‐1‐ylcarbonyl chloride derivatives are introduced as bench‐stable HCl surrogates for transfer hydrochlorination of terminal and internal alkenes as well as selected alkynes. The stepwise Grob fragmentation of those acyl chlorides into chloride, carbon monoxide, a low‐molecular‐weight arene, and a proton is promoted by B(C 6 F 5 ) 3 . This decarbonylative transfer process enables the addition of HCl across C−C double and triple bonds with Markovnikov selectivity at room temperature.

Topics & Concepts

ChemistryCarbon monoxideDecarbonylationVinyl chlorideHydrogen chlorideTriple bondFragmentation (computing)Double bondMarkovnikov's ruleChlorideSelectivityMedicinal chemistryOrganic chemistryPhotochemistryCatalysisComputer scienceCopolymerPolymerRegioselectivityOperating systemCatalytic C–H Functionalization MethodsOxidative Organic Chemistry ReactionsVanadium and Halogenation Chemistry
Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>‐Initiated Grob Fragmentation | Litcius