Iodine‐Promoted Tunable Synthesis of 2‐Naphthyl Thioethers and 1‐Naphthyl Thioethers

Abstract

An iodine‐promoted regioselective sulfenylation/deoxygenation/aromatization reaction of 1‐tetralones with disulfides has been developed. This process could be modified to synthesize 2‐naphthyl thioethers and 1‐naphthyl thioethers in moderate to excellent yields, respectively. Furthermore, when the reaction was extended to 2‐tetralones, 2‐naphthyl thioethers were obtained as the sole products. The current study bridges the deoxygenation and sulfenylation/aromatization of ketones, thus providing a new tool in organic synthesis.magnified image

Recent Advances in Iodine‐Promoted C−S/N−S Bonds Formation

“…In 2019, Yang and co‐workers reported an iodine‐mediated regioselective thiolation/deoxygenation/aromatization of 1‐tetralones 131 a with disulfides to selectively afford 2‐naphthyl and 1‐naphthyl thioethers in a tunable pathway (Scheme 43 a). [107a] This is really an interesting transformation. Through the radical trapping experiment and a crossover experiment performed by using a 1:1 mixture of polydeuterated 1‐tetralone and undeuterated 6‐methoxy‐1‐tetralone, it was confirmed the reaction should not involve a radical process and the hydrogen transfer might endure an intramolecular process.…”

Forging C−S(Se) Bonds by Nickel‐catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides

“…Notably, increasing the dppp loading to 40 mol % afforded the product 3 a in 80 % yield (entry 21). When no metal was added or only Mn was added in the reaction system, there was no or little decarbonylation product, but thioester was formed (entry [22][23]. When only Zn was added, 3 a was obtained with 45 % yield (entry 24).…”

“…(4‐methoxyphenyl)(naphthalen‐2‐yl)sulfane (3 f) [22] The title compound was isolated by column chromatography (eluent: EtOAc/petroleum ether=1/300) as a white solid (117 mg, 88 % yield). mp 67.7–69.0 °C.…”

“…(4‐(Tert‐butyl)phenyl)(naphthalen‐2‐yl)sulfane (3 i) [22] The title compound was isolated by column chromatography (petroleum ether) as a colorless oil (111 mg, 76 % yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.81–7.66 (m, 4H), 7.49–7.40 (m, 2H), 7.38 (d, J =8.6 Hz, 1H), 7.33 (s, 4H), 1.31 (s, 9H).…”

“…(2-methoxyphenyl)(naphthalen-2-yl)sulfane (3 e) [11] The title compound was isolated by column chromatography (eluent: EtOAc/ petroleum ether = 1/300) as a colorless oil (102 mg, 77 % yield). 1 (4-methoxyphenyl)(naphthalen-2-yl)sulfane (3 f) [22] The title compound was isolated by column chromatography (eluent: EtOAc/ petroleum ether = 1/300) as a white solid (117 mg, 88 % yield). mp 67.7-69.0°C.…”