Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 1, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202112575
Keywords
alkynes; DFT calculations; hydropentafluorosulfanylation; pentafluorosulfanyl chloride; radical reactions
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Funding
- Natural Sciences and Engineering Research Council of Canada (NSERC)
- OmegaChem
- Universite Laval
- New Jersey Institute of Technology (NJIT)
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This photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes uses SF5Cl and (TMS)(3)SiH as the hydrogen atom donor. It selectively generates (Z)-(1-alken-1-yl)pentafluoro-lambda(6)-sulfanes, allowing for the preparation of a previously unknown geometrical isomer. DFT calculations show that the selectivity is due to the preference of SF5-substituted vinylic radicals to adopt a cis geometry and increased steric contacts during transition structures leading to the minor (E)-products.
A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF5Cl and (TMS)(3)SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-lambda(6)-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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