O-Directed hydrostannation of β-cyclopropyl propargyl alcohol 22 with stannanes and cat. Et3B in THF/H2O or PhMe/MeOH fails to deliver any detectable products of α-stannylvinyl cation capture. Instead only α-stannyl-β-cyclopropylvinyl radical intermediates can be detected, which undergo fast H-atom abstraction and/or cyclopropane ring-opening as a result of eliminative β-scission.
|Media of output||ChemRxiv Database|
|Number of pages||4|
|Publication status||Published - 15 Jul 2019|
|Publisher||American Chemical Society|
- Stannylvinyl Cation
- O-Directed Free Radical Hydrostannation with Ph3SnH/cat. Et3B, Propargylically-Oxygenated Alkyl Acetylenes, Stannylvinyl Radical, b-Stannylvinyl cation, Vinylperoxy radical, Trisubstituted Stannylvinyl Radical H-Atom Abstraction, Vinylstannane isomerisation, Allylic 1,3-strain and 1,2-strain, Internal Ligand Enhanced Radicalophilicity, Ph3Sn radicals have higher electron affinity, The magnitudes of polar solvent rate accelerations observed for genuinely ionic reaction mechanisms
Hale, K. J., Watson, H. A., Manaviazar, S., & Steeds, H. G. (2019, Jul 15). Fast Ring-Opening of an Intermediary α-Stannyl-β-Cyclopropylvinyl Radical Does Not Support Formation of an α-Stannylvinyl Cation in the O-Directed Free Radical Hydrostannation of Dialkyl Acetylenes. https://chemrxiv.org/articles/Fast_Ring-Opening_of_an_Intermediary_-Stannyl-_-Cyclopropylvinyl_Radical_Does_Not_Support_Formation_of_an_-Stannylvinyl_Cation_in_the_O-Directed_Free_Radical_Hydrostannation_of_Dialkyl_Acetylenes/8867651