Fig. 2: Reagents synthesis and substrate scope of olefins.

A General procedure for synthesis of transfer reagents 4; B A general “Pentafluorosulfanylation” of olefins enabled by our transfer reagents and their substrate scopes. Unless otherwise noted, reactions in this table were performed at 0.1 mmol scale in methyl tert-butyl ether (MTBE, 0.1 M) under 390 nm LEDs for 1 h, using thioxanthone (10 mol%). Isolated yields are reported. Diastereomeric ratios were determined by NMR analysis of the crude reaction mixture. ^aPh₂CN-OH (1.0 equiv.), EDCI (1.0 equiv.), DCM (0.1 M); Ph₂CN-OH, benzophenone oxime; EDCI, 1-(3-Dimethylaminopropyl)−3-ethyl carbodiimide hydrochloride. ^bPPTS (2.0 equiv.), THF/H₂O (9:1, 0.05 M), 45 °C; PPTS, Pyridinium p-toluene sulfonate. ^cPd/C (10 wt%), dry MeOH (0.1 M), H₂ balloon. ^dReagent 4 (2.0 equiv.) was used. ^eThe low-concentration solution of Isobutylene in MTBE (0.084 M) was used. ^fIsobutylene balloon was used. ^gNMR yield. ^hPPTS (2.0 equiv.), THF/H₂O (9:1, 0.05 M), 40 °C. ⁱReagent 4 (1.2 equiv.) was used. See Supplementary Sections 2, 3, and 6 for experimental details.