Forging C–S Bonds through Nickel-Catalyzed Aryl Anhydrides with Thiophenols: Decarbonylation or Decarbonylation Accompanied by Decarboxylation

Abstract

A nickel-catalyzed decarbonylation or decarbonylation accompanied by decarboxylation cross-coupling reaction of aryl anhydrides with thiophenols as coupling partners was disclosed. This method is promoted by a commercially available, moisture-stable, and inexpensive nickel(II) precatalyst. The process can tolerate a variety of functional groups using ubiquitous aryl anhydrides as cross-coupling precursors to produce thioethers in moderate to excellent yields.

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

“…(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 H NMR (400 MHz, CDCl 3 ) δ 7.83 (s, 1H), 7.82–7.68 (m, 3H), 7.52–7.43 (m, 2H), 7.41 (d, J =8.6 Hz, 1H), 7.26 (d, J =8.1 Hz, 1H), 7.11 (d, J =7.4 Hz, 1H), 6.92 (d, J =8.1 Hz, 1H), 6.86 (t, J =7.3 Hz, 1H), 3.87 (s, 3H).…”

“…Naphthalen‐2‐yl(o–tolyl)sulfane (3 h) [11] The title compound was isolated by column chromatography (petroleum ether) as a colorless oil (115 mg, 92 % yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J =7.5 Hz, 1H), 7.73 (d, J =8.6 Hz, 1H), 7.70–7.61 (m, 2H), 7.48–7.39 (m, 2H), 7.36–7.27 (m, 2H), 7.27–7.19 (m, 2H), 7.15 (t, J =7.3 Hz, 1H), 2.40 (s, 3H).…”

“…(4‐Methoxyphenyl)(4‐(trifluoromethyl)phenyl)sulfane (4 q) [11] The title compound was isolated by column chromatography (petroleum ether) as a white solid (101 mg, 71 % yield). mp 83.5‐85.1 °C.…”

“…mp 105.4-107.1°C. (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).…”

“…In the same year, Rueping's research group disclosed a new and selective cross‐coupling reaction of esters and amides with mercaptans as coupling partners [10] . In 2019, our laboratory reported that under the catalysis of a stable nickel precatalyst, anhydride and thiophenol established C−S bonds through decarbonylation or decarbonylation followed by decarboxylation [11] . Most recently, Sanford et al.…”