Thiolate-assisted copper(i) catalyzed C–S cross coupling of thiols with aryl iodides: scope, kinetics and mechanism

Abstract

Transition metal catalyzed coupling of thiols with aryl iodide offers a convenient method for accessing C–S linkage in organic synthesis. Herein, we report an efficient and practical method for the...

Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

“…1 H NMR (400 MHz, CDCl 3 ) δ 7.34 (1H, dd, J = 7.7, 1.6 Hz), 7.17–7.21 (1H, m), 6.98 (1H, s), 6.83 (1H, d, J = 8.0 Hz), 6.71–6.76 (2H, m), 6.67 (1H, d, J = 8.0 Hz), 4.18 (2H, s), 2.37 (3H, s), 2.24 (3H, s); 13 C­{ 1 H} NMR (101 MHz, CDCl 3 ) δ 148.5, 136.8, 135.9, 135.5, 131.9, 131.3, 130.6, 127.5, 126.6, 119.0, 115.4, 115.2, 20.9, 20.2. Spectra were consistent with literature data …”

“…1 H NMR (400 MHz, CDCl 3 ) δ 7.38 (1H, d, J = 7.8 Hz), 7.15 (1H, s), 7.02–7.10 (3H, m), 6.83–6.87 (1H, m), 6.50 (1H, d, J = 8.6 Hz), 3.05 (8H, d, J = 4.9 Hz), 2.38 (3H, s), 2.36 (3H, s), 2.32 (3H, s); 13 C­{ 1 H} NMR (101 MHz, CDCl 3 ) δ 149.7, 142.6, 139.3, 136.4, 134.8, 131.8,128.1, 127.9, 126.2, 125.6, 124.4, 120.0, 53.1, 46.6, 21.3, 20.7. Spectra were consistent with literature data …”

“…Spectra were consistent with literature data. 35 Procedure for Reductive Cross-Coupling Thiolation of Methyl 4-Bromobenzoate. A 120 °C oven-dried 25 mL glass Schlenk, equipped with a stirring bar, was charged with methyl 4bromobenzoate 1o (103.0 mg, 0.500 mmol, 1.00 equiv), Nthiosuccinimides (0.750 mmol,1.50 equiv), Zn (98.1 mg, 1.50 mmol, 3.00 equiv), NaI (150.0 mg, 1.00 mmol, 2.00 equiv), NiBr 2 (10.9 mg, 0.0500 mmol, 0.050 equiv), and 1,10-phenanthroline (18.0 mg, 0.100 mmol, 0.200 equiv).…”

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…The performed kinetic and computational studies support a Cu(I)/Cu(III) catalytic cycle with K[Cu(SPh) 2 ] as catalytically active species. Scheme 7 Cu-catalyzed coupling of thiols with aryl iodides 39 The thiolation of less reactive aryl chlorides was investigated in a broader scope by Lee and co-workers, in addition to other aryl halides (Scheme 8). 40 The transformation was performed using a catalytic system consisting of CuI and oxalic diamide ligand L5, which enabled coupling of aromatic and aliphatic thiols.…”

“…38 A ligand free catalysis using CuI and KO t Bu for the coupling of aryl iodides with (hetero)aryl thiols in H 2 O/DME or ethanol as solvent was reported by the Patil group (Scheme 7). 39 Benzothiazole underwent a base-mediated ring opening to 2-aminobenzenethiolate, which entered the catalytic cycle to generate 2-amino-substituted diaryl sulfides. The performed kinetic and computational studies support a Cu(I)/Cu(III) catalytic cycle with K[Cu(SPh) 2 ] as catalytically active species.…”