Hydrostibination of Alkynes: A Radical Mechanism*

The addition of Sb-H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov Z-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring open-shell neutral intermediates. Density-functional theory (DFT) calculations are consistent with this model, predicting an activation barrier that is in agreement with the experimental value (Eyring analysis) and a rate limiting step that is congruent with the experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb^II and Sb^III intermediates to yield the observed Z-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a synthetic methodology.