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

Hamish A Watson; Soraya Manaviazar; Hannah G Steeds; Karl J Hale

doi:10.1039/c9cc05492h

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

Hamish A Watson, Soraya Manaviazar, Hannah G Steeds, Karl J Hale

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

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Abstract

O-Directed hydrostannation of b-cyclopropyl propargyl alcohol 22 with stannanes and cat. Et₃B in THF/H₂O or PhMe/MeOH fails todeliver any detectable products of α-stannylvinyl cation capture. Instead only α-stannyl-β-cyclopropylvinyl radical intermediates canbe detected, which undergo fast H-atom abstraction and/or cyclopropane ring-opening as a result of eliminative β-scission.

Original language	English
Number of pages	4
Journal	Chemical Communications
DOIs	https://doi.org/10.1039/c9cc05492h
Publication status	Published - 15 Nov 2019

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10.1039/c9cc05492hLicence: CC BY

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
Copyright 2019 the authors. This is an open access article published under a Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Final published version, 2.9 MBLicence: CC BY

Further investigations into the mechanism of the o-directed free radical hydrostannation of alkyl and aryl acetylenes
Watson, H. (Author), Stevenson, P. (Supervisor) & Hale, K. (Supervisor), Jul 2022
Student thesis: Doctoral Thesis › Doctor of Philosophy

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title = "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",

abstract = "O-Directed hydrostannation of b-cyclopropyl propargyl alcohol 22 with stannanes and cat. Et3B in THF/H2O or PhMe/MeOH fails todeliver any detectable products of α-stannylvinyl cation capture. Instead only α-stannyl-β-cyclopropylvinyl radical intermediates canbe detected, which undergo fast H-atom abstraction and/or cyclopropane ring-opening as a result of eliminative β-scission.",

author = "Watson, {Hamish A} and Soraya Manaviazar and Steeds, {Hannah G} and Hale, {Karl J}",

year = "2019",

month = nov,

day = "15",

doi = "10.1039/c9cc05492h",

language = "English",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

}

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. / Watson, Hamish A; Manaviazar, Soraya; Steeds, Hannah G et al.
In: Chemical Communications, 15.11.2019.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Watson, Hamish A

AU - Manaviazar, Soraya

AU - Steeds, Hannah G

AU - Hale, Karl J

PY - 2019/11/15

Y1 - 2019/11/15

N2 - O-Directed hydrostannation of b-cyclopropyl propargyl alcohol 22 with stannanes and cat. Et3B in THF/H2O or PhMe/MeOH fails todeliver any detectable products of α-stannylvinyl cation capture. Instead only α-stannyl-β-cyclopropylvinyl radical intermediates canbe detected, which undergo fast H-atom abstraction and/or cyclopropane ring-opening as a result of eliminative β-scission.

AB - O-Directed hydrostannation of b-cyclopropyl propargyl alcohol 22 with stannanes and cat. Et3B in THF/H2O or PhMe/MeOH fails todeliver any detectable products of α-stannylvinyl cation capture. Instead only α-stannyl-β-cyclopropylvinyl radical intermediates canbe detected, which undergo fast H-atom abstraction and/or cyclopropane ring-opening as a result of eliminative β-scission.

U2 - 10.1039/c9cc05492h

DO - 10.1039/c9cc05492h

M3 - Article

SN - 1359-7345

JO - Chemical Communications

JF - Chemical Communications

ER -

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

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Further investigations into the mechanism of the o-directed free radical hydrostannation of alkyl and aryl acetylenes

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