Photoinitiated <i>anti</i>‐Hydropentafluorosulfanylation of Terminal Alkynes
Mélodie Birepinte, Pier Alexandre Champagne, Jean‐François Paquin
Abstract
Abstract A photoinitiated anti ‐hydropentafluorosulfanylation of terminal alkynes using SF 5 Cl and (TMS) 3 SiH as the hydrogen atom donor is reported. This transformation generates selectively ( Z )‐(1‐alken‐1‐yl)pentafluoro‐λ 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 SF 5 ‐substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor ( E )‐products.
Topics & Concepts
Steric effectsChemistryRadicalSelectivityTerminal (telecommunication)StereochemistryTransition stateHydrogen atomPhotochemistryMedicinal chemistryCatalysisOrganic chemistryTelecommunicationsComputer scienceAlkylFluorine in Organic ChemistrySulfur-Based Synthesis TechniquesInorganic Fluorides and Related Compounds