Photoinitiated anti‐Hydropentafluorosulfanylation of Terminal Alkynes

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 ge...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-01, Vol.61 (1), p.e202112575-n/a
Main Authors: Birepinte, Mélodie, Champagne, Pier Alexandre, Paquin, Jean‐François
Format: Article
Language:English
Subjects:
Alkynes
DFT calculations
hydropentafluorosulfanylation
pentafluorosulfanyl chloride
radical reactions
Selectivity
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Summary: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. The direct synthesis of new (Z)‐(1‐alken‐1‐yl)pentafluoro‐λ6‐sulfanes was performed via the photoinitiated anti‐hydropentafluorosulfanylation of terminal alkynes. The reaction of SF5Cl with 24 substrates in the presence of (TMS)3SiH as a H‐atom donor gave access to the undocumented Z‐isomer. The origins of this unusual selectivity were investigated by DFT calculations, which provide a better understanding of the geometry and reactivity of SF5‐substituted vinylic radicals.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202112575