Facile Thiol–Ene Click Protocol Using Benzil as Sensitizer and White LED as Light Source

Abstract

The thiol–ene reaction leading to a series of thioether derivatives by simple metal and oxidant free visible light promoted photosensitized protocol, following anti‐Markonikov hydrothiolation of unactivated aryl and alkyl olefins at room temperature is demonstrated. Benzil served as a green photosensitizer in this reaction and white LED lights as a light source. This radical based thiol–ene reaction is operationally simple and tolerates a wide variety of functional groups present in olefins.

Tuning Selectivity in the Visible-Light-Promoted Coupling of Thiols with Alkenes by EDA vs TOCO Complex Formation

“…Colorless Liquid; yield: 25%; 1 H NMR (500 MHz, CDCl 3 ) δ 7.37 (d, J = 8.1 Hz, 2H), 7.32–7.29 (m, 4H), 7.24–7.18 (m, 4H), 3.18 (t, J = 7.6 Hz, 2H), 2.94 (t, J = 8.3 Hz, 2H). Spectral data are in agreement with literature values …”

“…Spectral data are in agreement with literature values. 32 (4-Methylphenethyl)(phenyl)sulfane (5j). Colorless Liquid; yield: 30%; 1 H NMR (500 MHz, CDCl 3 ) δ 7.35 (d, J = 8.1 Hz, 2H), 7.30 (t, J = 7.7 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 7.12− 7.08 (m, 4H), 3.15 (d, J = 7.7 Hz, 2H), 2.89 (d, J = 8.3 Hz, 2H), 2.33 (s, 3H).…”

“…Spectral data are in agreement with literature values. 32 Control Experiment Synthesis Procedure of (1-Phenylethane-1,2-diyl)bis(phenylsulfane) (6a). An oven-dried glass…”

“…Spectral data are in agreement with literature values. 32 Methyl 2-Methyl-3-(phenylthio)propanoate (5t). Colorless Liquid; yield: 9%; 1 H NMR (500 MHz, CDCl 3 ) δ 7.36 (d, J = 7.3 Hz, 2H), 7.28 (t, J = 7.3 Hz, 2H), 7.20 (t, J = 7.2 Hz, 1H), 3.66 (s, 3H), 3.28−3.24 (m, 1H), 2.94−2.90 (m, 1H), 2.73− 2.66 (m, 1H), 1.26 (d, J = 6.8 Hz, 3H).…”

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

“…Depending on the X-element carrying the oxo moiety, PCs HAT can be grouped within different families (Figure ). These comprise the class of carbonyl derivatives (Z = C), , encompassing simple (aromatic) ketones and aldehydes, − α-diketones, α-ketoacids, and (anthra)­quinones, − as well as the xanthene dye Eosin Y. , On the other hand, inorganic derivatives including the decatungstate anion [W 10 O 32 ] 4– (Z = W) ,− and the uranyl cation [UO 2 ] 2+ (Z = U) , as well as antimony oxo porphyrin complexes (Z = Sb) have been likewise proposed as PCs HAT . A notable exception of PC HAT lacking the oxo group is known, namely the electrogenerated tris­(amino)­cyclopropenium (TAC) radical dication …”