H
A. N. Dinh et al.
Cluster
Synlett
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Ru(bpy)3Cl2 (5 mol%), Na2S2O8 (2.0 equiv), and pyridine (2.0
equiv) were added to a solution of 1:1 MeCN/H2O (25 mg/1 mL).
The reaction was stirred under blue LEDs for 12 h at room tem-
perature. The resulting solution was quenched with H2O,
extracted with EtOAc, dried over Na2SO4, and concentrated in
vacuo. The product was purified via FCC and prep TLC with gra-
dient from hexanes to 8:2 Hex/EtOAc.
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42, 1077.
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General Procedure for the Synthesis of Sulfenylated Indoles
In a 10 mL scintillation vial, substituted indole (1.0 equiv),
{Ir[dF(CF3)ppy]2(dtbpy)}PF6 photocatalyst (1 mol%), Na2S2O8
(2.0 equiv), KOH (2.0 equiv), and thiophenol (1.2 equiv) were
added to a solution of 1:1 MeCN/H2O (25 mg/1 mL). The reac-
tion was left to stir under blue LEDs for 12 h at room tempera-
ture. The resulting solution was quenched with H2O and
extracted with EtOAc, dried over Na2SO4, and concentrated in
vacuo. The product was purified via FCC and prep TLC (8:2
Hex/EtOAc). Melatonin substrates were purified via FCC with
(2:8 Hex/EtOAc).
(18) Nalbandian, C. J.; Miller, E. M.; Toenjes, S. T.; Gustafson, J. L.
Chem. Commun. 2017, 53, 1494.
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81, 6898.
2-(tert-Butyl)benzo[d]thiazole (1b)
57% with no pyridine, 79% with pyridine, off-white solid. 1H
NMR (500 MHz, CDCl3): = 8.00 (dt, J = 8.2, 0.9 Hz, 1 H), 7.85
(dd, J = 8.0, 0.45 Hz, 1 H), 7.44 (ddd, J = 8.3, 7.2, 1.3 Hz, 1 H), 7.34
(ddd, J = 8.2, 7.2, 1.2 Hz, 1 H), 1.53 (s, 9 H). The spectral data are
in agreement with the reported literature.37 MS-APCI: m/z
calcd: C11H13NS [M + H]+ 192.3; found: 192.1.
(23) Smith, J. M.; Harwood, S. J.; Baran, P. S. Acc. Chem. Res. 2018, 51,
1807.
2-(tert-Butyl)napthol[1,2-d]thiazole (6b)
(24) Zhang, G.; Liu, C.; Yi, H.; Meng, Q.; Bian, C.; Chen, H.; Jian, J.; Wu,
L.; Lei, A. J. Am. Chem. Soc. 2015, 137, 9273.
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Fan, X. RSC Adv. 2017, 7, 37739.
55% with no pyridine, 54% with pyridine, yellow-green solid. 1H
NMR (500 MHz, CDCl3): = 8.82 (dt, J = 8.0, 0.8 Hz, 1 H), 7.93 (d,
J = 8.1 Hz, 1 H), 7.87 (d, J = 8.7 Hz, 1 H), 7.75 (d, J = 8.7 Hz, 1 H),
7.65 (ddd, J = 8.2, 6.9, 1.3 Hz, 1 H), 7.55 (ddd, J = 8.2, 6.9, 1.3 Hz,
1 H), 1.59 (s, 9 H). 13C NMR (101 Hz, CDCl3): = 180.7, 149.2,
131.8, 131.2, 128.6, 127.9, 126.6, 125.7, 125.0, 124.0, 119.0,
38.4, 31.0. MS-APCI: m/z calcd for C15H15NS [M+H]+: 242.4;
found: 242.1.
(28) Das, A.; Maity, M.; Malcherek, S.; König, B.; Rehbein, J. Beilstein J.
Org. Chem. 2018, 14, 2520.
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Dempsey, J. L. J. Chem. Educ. 2017, 95, 197.
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D. ACS Catal. 2019, 9, 3322.
(32) Cruz, C. L.; Nicewicz, D. A. ACS Catal. 2019, 9, 3926.
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2880.
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114, 2587.
N-{2-[5-Methoxy-2-(p-tolylthio)-1H-indol-3- yl]ethyl}acet-
amide (18b)
68%, tan solid. 1H NMR (400 MHz, CDCl3): = 8.12 (s, 1 H), 7.22
(d, 8.8 Hz, 1 H), 7.02–7.06 (m, 3 H), 6.98 (d, 8.3 Hz, 2 H), 6.91
(dd, J = 8.8, 2.4 Hz, 1 H), 5.50 (s, 1 H), 3.86 (s, 3 H), 3.52 (q, J = 6.4
Hz, 2 H), 3.05 (t, J = 6.5 Hz, 2 H), 2.27 (s, 3 H), 1.78 (s, 3 H). 13C
NMR (126 Hz, CDCl3): = 170.28, 154.36, 136.17, 133.22,
132.07, 130.04, 128.13, 127.00, 123.50, 119.64, 114.32, 111.93,
100.32, 55.87, 40.01, 24.75, 23.13, 20.89. MS-APCI: m/z calcd for
C
20H22N2O2S [M + H]+: 355.5; found: 355.5
(37) Zhang, G.; Liu, C.; Yi, H.; Meng, Q.; Bian, C.; Chen, H.; Jian, J. X.;
(36) General Procedure for Synthesis of Substituted Benzothi-
azoles
Wu, L. Z.; Lei, A. J. Am. Chem. Soc. 2015, 137, 9273.
In a 10 mL scintillation vial, thioabenzamide (1.0 equiv),
© 2019. Thieme. All rights reserved. — Synlett 2019, 30, A–H