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(C6F5)3. This decarbonylative transfer process enables the addition of HCl across C−C double and triple bonds with Markovnikov selectivity at room temperature.
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