TY - JOUR
T1 - Photoinitiated anti-Hydropentafluorosulfanylation of Terminal Alkynes
AU - Birepinte, Mélodie
AU - Champagne, Pier Alexandre
AU - Paquin, Jean François
N1 - Funding Information:
We acknowledge the financial support of the Natural Sciences and Engineering Research Council of Canada (NSERC), OmegaChem, Université Laval, and the New Jersey Institute of Technology (NJIT). Calculations were performed on the Lochness cluster at NJIT. We thank Dr. Chloé Batisse for the preliminary results.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2022/1/3
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.
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U2 - 10.1002/anie.202112575
DO - 10.1002/anie.202112575
M3 - Article
C2 - 34716642
AN - SCOPUS:85119887291
SN - 1433-7851
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 1
M1 - e202112575
ER -