Photoinitiated anti-Hydropentafluorosulfanylation of Terminal Alkynes

Mélodie Birepinte; Pier Alexandre Champagne; Jean François Paquin

doi:10.1002/anie.202112575

Photoinitiated anti-Hydropentafluorosulfanylation of Terminal Alkynes

Mélodie Birepinte
, Pier Alexandre Champagne
, Jean François Paquin

Chemistry and Environmental Science

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

51 Scopus citations

Abstract

A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF₅Cl and (TMS)₃SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-λ⁶-sulfanes (Z:E : >85:15), thus allowing the preparation of this previously unknown geometrical isomer. DFT calculations highlight that the selectivity is due to the intrinsic preference of SF₅-substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor (E)-products.

Original language	English (US)
Article number	e202112575
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	1
DOIs	https://doi.org/10.1002/anie.202112575
State	Published - Jan 3 2022

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

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10.1002/anie.202112575

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title = "Photoinitiated anti-Hydropentafluorosulfanylation of Terminal Alkynes",

abstract = "A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF5Cl and (TMS)3SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-λ6-sulfanes (Z:E : >85:15), thus allowing the preparation of this previously unknown geometrical isomer. DFT calculations highlight that the selectivity is due to the intrinsic preference of SF5-substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor (E)-products.",

author = "M{\'e}lodie Birepinte and Champagne, \{Pier Alexandre\} and Paquin, \{Jean Fran{\c c}ois\}",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2022",

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doi = "10.1002/anie.202112575",

language = "English (US)",

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AU - Birepinte, Mélodie

AU - Champagne, Pier Alexandre

AU - Paquin, Jean François

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Y1 - 2022/1/3

N2 - A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF5Cl and (TMS)3SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-λ6-sulfanes (Z:E : >85:15), thus allowing the preparation of this previously unknown geometrical isomer. DFT calculations highlight that the selectivity is due to the intrinsic preference of SF5-substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor (E)-products.

AB - A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF5Cl and (TMS)3SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-λ6-sulfanes (Z:E : >85:15), thus allowing the preparation of this previously unknown geometrical isomer. DFT calculations highlight that the selectivity is due to the intrinsic preference of SF5-substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor (E)-products.

UR - https://www.scopus.com/pages/publications/85119887291

UR - https://www.scopus.com/pages/publications/85119887291#tab=citedBy

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DO - 10.1002/anie.202112575

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ER -

Photoinitiated anti-Hydropentafluorosulfanylation of Terminal Alkynes

Abstract

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