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Article

Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles

by
Mio Matsumura
,
Airi Umeda
,
Yuika Sumi
,
Naoki Aiba
,
Yuki Murata
and
Shuji Yasuike
*
School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, Japan
*
Author to whom correspondence should be addressed.
Molecules 2024, 29(13), 3227; https://doi.org/10.3390/molecules29133227
Submission received: 19 June 2024 / Revised: 3 July 2024 / Accepted: 3 July 2024 / Published: 8 July 2024
(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)
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Abstract

:
Heterocyclic aryl selenides have recently attracted considerable research interest owing to their applications in biological and pharmaceutical fields. Herein, we describe a simple and general synthesis of 3-selanylindoles via a novel regioselective C–H selenation of indoles using a bismuth reagent as a catalyst. The reactions of indoles with diselenides in the presence of 10 mol% BiI3 at 100 °C in DMF afforded the corresponding 3-selanylindoles in moderate-to-excellent yields. The reaction proceeded efficiently under aerobic conditions by adding only a catalytic amount of BiI3, which was non-hygroscopic and less toxic, and both selanyl groups of the diselenide were transferred to the desired products.

Graphical Abstract

1. Introduction

Organoselenium compounds have received considerable attention in organic chemistry, as well as in biological and pharmaceutical sciences [1,2,3,4,5,6,7,8,9,10,11,12,13,14], and there is growing interest in biologically active unsymmetrical diaryl selenides containing heterocyclic rings (i.e., aryl heteroaryl selenides). For example, 3-selanylindoles, compounds with a selenium side chain substituted at the 3-position of indoles, which are widely used as a basic skeleton in natural products and medicines, have been reported to have biological activities, such as the inhibition of tubulin polymerization, antiproliferative activity, anti-inflammatory properties, and antioxidant activity, and are expected to be used as drug discovery resources (Figure 1) [15,16,17,18,19,20]. Therefore, the development of synthetic methods for these compounds has attracted attention. Direct selenation into indoles has been reported since the 2010s and is a powerful and commonly used method involving the reaction of available indole derivatives with stable and easy-to-handle diselenides as selenium sources. These reactions can be broadly classified into those involving the addition of oxidants [21,22,23] or bases [24,25,26], radical reactions using photoreactors [27,28,29,30,31,32,33,34] or electrolytic devices [35,36], and those using transition metal catalysts containing Pd, Cu, Ag, and Fe [37,38,39,40,41,42]. However, these reactions use excessive reagents, additives, and transition metal catalysts of toxicological concern even in catalytic reactions, and require special equipment and expensive photocatalysts or supporting electrolytes for the photoreactions and electrolytic reactions, respectively. Recently, four transition metal-free catalytic reactions were reported (Scheme 1). Braga et al. developed a catalytic reaction using DMSO as the oxidant in the presence of a catalytic quantity of I2; however, the reaction required microwave irradiation [43]. The researchers also used KIO3 as a catalyst, but this reaction required an excess (4 equiv.) of glycerol [44]. Roehrs et al. reported an I2-catalyzed reaction that required the addition of stoichiometric amounts of urea hydrogen peroxide as an oxidant [45]. Jana et al. developed a reaction using Cs2CO3 as a catalyst, albeit in an oxygen atmosphere [46]. As mentioned above, catalytic reactions require additives; otherwise, the reaction conditions are restrictive.
Inorganic bismuth compounds have attracted attention in the field of organic synthesis since the 1980s because of their excellent reactivity as mild Lewis acids, nontoxicity, and environmental friendliness [47,48,49,50,51,52]. For example, BiCl3, a trivalent bismuth halide, has been reported to act as a catalyst for the following reactions: the Mukaiyama aldol reaction [53,54], the nucleophilic opening of epoxide [55], deoxygenative allylation [56], the Diels–Alder reaction [57,58], the three-component reaction of aldehydes, amines, and ketones or trimethylsilyl cyanide [59,60], the Friedel–Crafts reaction [61], the oxy-Michael addition [62], the aminooxygenation of propargyl amidine [63], and the tandem cyclization of tryptamine-ynamide [64]. More recently, BiCl3 has been utilized in the catalytic coupling reactions of aryl iodides or aminobenzimidazoles with arylboronic acids for C(Ar)–C(Ar) and C(Ar)–N bond formation [65,66]. By contrast, bismuth iodide (BiI3) is widely used in semiconductors and solar cell devices [67,68]. However, its chemical reactivity in organic reactions is largely unknown, and its use in catalytic reactions has been limited to the deprotection of acetals, guanylation with desulfurization using thioureas and amines, and S,S-acetalization of benzaldehyde [69,70,71]. Inspired by these reports, we present a facile Bi(III)-catalyzed regioselective C(Ar)–Se bond formation reaction of indoles with diaryl diselenides using BiI3 as the catalyst for the synthesis of 3-selanylindoles under mild conditions. The system was simple, containing only substrates and a Bi catalyst.

2. Results and Discussion

We initially focused on determining the optimal experimental conditions, including screening for suitable catalysts and solvents, for the synthesis of 3-selanylindole 3aa using N-methylindole 1a and diphenyl diselenide 2a as model substrates, the results of which, are summarized in Table 1. N-methylindole 1a (0.5 mmol) was reacted with 2a (0.25 mmol) in the presence of several Bi catalysts (0.05 mmol) in DMF at 100 °C under aerobic conditions (entries 1–7). BiCl3, BiBr3, BiI3, and Bi(OTf)3, which function as Lewis acids, afforded the corresponding 3-selanylindole 3aa in good-to-excellent yields (77–97%). BiI3 displayed the best yield and reaction time, and both selanyl groups were efficiently transferred from the diselenide to product 3aa (entry 3). Furthermore, although bismuth halides such as BiCl3 and BiBr3 are hygroscopic, BiI3 can be easily handled in air without such concerns. By contrast, antimony catalysts with the same group of atoms as bismuth and other Lewis acid catalysts were less effective than BiI3 (entries 8–12). A comparison to iodine (I2) was also attempted; however, the reaction barely progressed (entry 13). Solvent screening indicated that the reaction proceeded efficiently in DMF (97%), DMSO (89%), and THF (60%), whereas CH3CN, MeOH, dioxane, 1,2-DCE, and toluene were inefficient (entries 3 and 14–20). When the reaction was performed at 60 °C, the reaction time increased markedly to 8 h (entry 21). The reaction performed under oxygen produced 3aa in a high yield (94%), which was almost identical to that obtained under aerobic conditions (entries 3 and 22). However, the yield was notably suppressed (9%) under an argon atmosphere (entry 23). Decreasing the BiI3 loading from 10 to 5 and 1 mol% markedly prolonged the reaction time, although the reaction afforded the desired product (entries 24 and 25). The best result was obtained under aerobic conditions at 100 °C when 1a was treated with 0.5 equivalents of diselenide 2a in the presence of BiI3 (10 mol%) in DMF (entry 3). This selenation could also be scaled up to 10 mmol. The desired product 3aa was obtained in an excellent yield (99%), generating up to 2.84 g of the product. Furthermore, the reaction of 1a and 2a with 1 equivalent of TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] or 1,1-diphenylethylene as radical scavengers afforded 3aa in yields of 94% and 96%, respectively (entries 26 and 27). These results indicate that the reaction system does not follow a radical mechanism. The regiochemistry of 3-selanylindole 3aa was elucidated using 1H-NMR and single-crystal X-ray analyses (Figure 2). The 1H-NMR spectrum of 3aa was consistent with that of the standard sample [41].
To understand the scope and limitations of the developed regioselective selenation reaction, various indoles 1 (0.5 mmol) were reacted with diselenides 2 (0.25 mmol) under the optimized conditions (Figure 3). The reaction of N-methylindole 1a with diaryl diselenides 2b–i afforded the corresponding products, i.e., 3ab–ai, in good-to-excellent yields, except for 3ah. For 3ab–ae, the presence of an electron-donating or electron-withdrawing group at the 4-position of the benzene ring of diselenides 3b–e did not affect the reaction progression, although the reaction time was slightly prolonged when electron-donating groups were substituted. Sterically hindered ortho-substituted diselenides 2f and 2g reacted to give selenides 3af and 3ag, respectively. By contrast, for 2h, which comprises a benzylamino group, the reaction did not proceed, and the starting materials were recovered. For the reaction using diaryl diselenide 2i, which bears a heterocyclic ring, 3ai was afforded in a good yield. Dibenzyl diselenide 2j, which contains a benzyl moiety as the alkyl group, also afforded 3aj in a good yield (82%). Next, the reaction of diphenyl diselenide 2a with various N-methylindoles, i.e., 1b–i, bearing electron-donating or electron-withdrawing groups on the benzene ring afforded the desired products 3ba–3ia in satisfactory yields (75–99%). The reaction proceeded smoothly from the unsubstituted indoles 1j–l to obtain the parent 3-selanylindoles 3ja–la (79–93%). Furthermore, the reaction of the N-substituted indoles 1m and 1n with benzyl or phenyl groups on the nitrogen also gave the corresponding products 3ma and 3na; however, N-acetylindole 1o with an electron-withdrawing group did not give 3oa, and the starting materials were recovered. These results suggest that the reaction is electrically influenced by the substituents on the indole nitrogen. 2-Phenyl- and 2-methylindoles 1p and 1q were treated with 2a to afford the 3-selanyl-2-substituted indoles 3pa and 3qa, respectively. The attempted double selenation of 1a using two equivalents of diphenyl diselenide 2a did not yield the corresponding 2,3-diselanylindole 3ra; instead, 3-selanylindole 3aa was isolated in a yield of 98%. These results suggest that this reaction proceeds only at the 3-position of the indole. Finally, the reaction of 1a with dichalcogenides containing sulfur and tellurium was attempted. The reaction with diphenyl disulfide afforded the desired 3-sulfanylindole 4 in an excellent yield (99%), although the reaction time (24 h) was longer than that with diselenide, which is a selenium reagent. By contrast, the reaction proceeded to a certain extent with diphenyl ditelluride, and indole 5 was obtained in a yield of 26%.
However, the reaction mechanism for this selenation remains unclear. Circumstantial evidence indicates that the reaction was affected by the gaseous atmosphere and proceeded smoothly in the presence of a molecular oxygen atmosphere while being notably suppressed in an inert gas atmosphere (Table 1: entries 3, 22, and 23). BiI3 forms a pentacoordinated complex with bismuth, the central atom, and the oxygen atoms of reagents and solvents such as Mo8O26 and THF [72,73]. Therefore, a possible mechanism for this reaction is illustrated in Scheme 2. The initial step was the generation of the pentacoordinated Bi–peroxo complex A from BiI3 and oxygen. While the selenium atom of the diselenide coordinates with complex A, the 3-position of the indole nucleophilically attacks another selenium atom, forming complex B and intermediate C. The aryl selenide anion formed during the interconversion between complexes B and A attacks intermediate C to form 3-selanylindole 3 and selenol D. Selenol D is converted to diselenide 2 via oxidation in air. Therefore, the reaction proceeds with 0.5 equivalents of diselenide, and both selanyl groups are used for the reaction. Bismuth complexes A and B, which are expected to form during this process, have not yet been confirmed or isolated.

3. Conclusions

Herein, we report a simple Bi-catalyzed regioselective selenation protocol for the synthesis of 3-selanylindoles under mild reaction conditions. The reaction is atom-economical, with the participation of both selanyl groups of the diaryl diselenide. Indoles and diselenides bearing different functional groups afforded the corresponding products in satisfactory yields. This reaction is the first example of the Bi-catalyzed C–H selenation of aromatic heterocycles. Detailed studies on the exact mechanism of this reaction and the synthesis of asymmetric selenides containing other heterocyclic rings using this protocol are currently underway.

4. Materials and Methods

4.1. General Information

All the chemicals, including organic solvents, were obtained from commercial vendors and used as received without further purification. All chromatographic separations were accomplished with Silica Gel 60N (Kanto Chemical Co., Inc., Tokyo, Japan). Thin-layer chromatography (TLC) was performed using Macherey–Nagel Pre-coated TLC plates Sil G25 UV254. Melting point measurements were conducted on a Yanagimoto micro-melting point hot-stage apparatus (MP-S3) and reported as uncorrected values. In addition, 1H NMR (TMS: δ = 0.00 ppm as an internal standard), 13C NMR (CDCl3: δ = 77.00 ppm as an internal standard), 19F NMR (376 MHz, benzotrifluoride; δ = −64.0 ppm as an external standard), and 77Se NMR (76 MHz, diphenyldiselenide; δ = 463.15 ppm as an external standard) spectra were recorded on JEOL ECZ-400S (400, 100, 376, and 76 MHz for 1H-, 13C-, 19F-, and 77Se NMR, respectively) spectrometers (JEOL Ltd., Tokyo, Japan). GC-MS (EI) spectra were recorded on Agilent 5977 E Diff-SST MSD-230 V spectrometer. HRMS (ESI) spectra were recorded on Agilent 6230 (Agilent Technologies Japan, Ltd., Tokyo, Japan). X-ray measurements were recorded on Rigaku XtaLAB Synergy with a HyPix3000 diffractometer (Rigaku, Corp., Tokyo, Japan). IR spectra were recorded on an FTIR-8400S or IRAffinity-1S system from a Shimadzu spectrometer (SHIMADZU Corp, Kyoto, Japan) and are reported as the frequencies of absorption (cm−1). Only selected IR absorbencies are reported. The spectroscopic data of the calcogenated indoles 3aa–ad, 3ag, 3ka, 3ma, 3qa, 4 [41], 3aj [74], 3ba [42], 3ea, 3ja, 3na [35], 3la [27], 3pa [75], and 5 [76] are in accordance with those in the literature, and their characterization data are in Supplementary Materials.

4.2. General Procedure for the Synthesis of Calcogenated Indoles

The indole derivative (1) (0.5 mmol) was added to a solution of dichalcogenide (2) (0.25 mmol, 0.5 eq.) and bismuth(III) iodide (30 mg, 0.05 mmol, and 10 mol%) in anhydrous dimethylformamide (2 mL). After stirring at 100 °C in an oil bath, the mixture was cooled to room temperature and evaporated to dryness under reduced pressure. The crude product was purified on a silica gel column chromatography to give the desired product 3.

4.3. Characterization Data of Novel Compounds

4.3.1. 3-(4-Trifluoromethylphenyl)selanyl-1-methyl-1H-indole (3ae)

Yield: 171 mg (96%); Colorless prism (from CH2Cl2-Hexane); m.p. 133.0–135.0 °C; Rf = 0.54 (CH2Cl2-Hexane, 1:2). 1H NMR (400 MHz, CDCl3): δ = 7.57 (d, J = 7.8 Hz, 1H; Ar-H), 7.41 (d, J = 8.2 Hz, 1H; Ar-H), 7.36 (s, 1H; Ar-H), 7.35–7.30 (m, 3H; Ar-H), 7.26 (d, J = 8.2 Hz, 2H; Ar-H), 7.19 (td, J = 8.2, 0.9 Hz, 1H; Ar-H), 3.88 ppm (s, 3H; N-CH3). 13C NMR (100 MHz, CDCl3): δ = 140.0 (C), 137.5 (C), 135.9 (CH), 130.4 (C), 128.0 (CH), 127.5 (q, J = 32 Hz, C), 125.5 (q, J = 3.9 Hz, CH), 124.2 (q, J = 272 Hz, C), 122.7 (CH), 120.7 (CH), 120.2 (CH), 109.7 (CH), 94.6 (C), 33.2 ppm (CH3). 19F NMR (376 MHz, CDCl3): δ = −63.7 ppm. 77Se NMR (76 MHz, CDCl3): δ = 223.4 ppm. IR (ATR): ν~ = 739, 822, 1072, 1105, 1321 cm−1. MS (EI, 70 eV): m/z (%) = 355 (21) [M]+, 275 (100), 130 (14). HRMS (ESI): m/z calcd for C16H12F3NSe: 355.0087 [M]+; found: 355.0088.

4.3.2. 1-Methyl-3-(2-methylphenyl)selanyl-1H-indole (3af)

Yield: 129 mg (86%); Colorless plate (from CH2Cl2-Hexane); m.p. 129.0–132.0 °C; Rf = 0.20 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.59 (d, J = 7.8 Hz, 1H; Ar-H), 7.39 (d, J = 8.2 Hz, 1H; Ar-H), 7.31 (s, 1H; Ar-H), 7.30 (td, J = 8.2, 0.9 Hz, 1H; Ar-H), 7.17 (td, J = 7.3, 0.9 Hz, 1H; Ar-H), 7.10 (d, J = 7.3 Hz, 1H; Ar-H), 7.00 (td, J = 7.8, 2.3 Hz, 1H; Ar-H), 6.86–6.80 (m, 2H; Ar-H), 3.85 (s, 3H; N-CH3), 2.46 ppm (s, 3H; CH3). 13C NMR (100 MHz, CDCl3): δ = 137.6 (C), 135.92 (C), 135.87 (CH), 134.8 (C), 130.8 (C), 129.7 (CH), 127.8 (CH), 126.4 (CH), 125.2 (CH), 122.4 (CH), 120.5 (CH), 120.4 (CH), 109.5 (CH), 94.9 (C), 33.1 (CH3), 21.2 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 178.3 ppm. IR (ATR): ν~ = 411, 426, 729, 746, 1456 cm−1. MS (EI, 70 eV): m/z (%) = 301 (40) [M]+, 221 (60), 131 (100), 91 (30). HRMS (ESI): m/z calcd for C16H15NSe: 301.0370 [M]+; found: 301.0370.

4.3.3. 3-(2-Benzothienyl)selanyl-1-methyl-1H-indole (3ai)

Yield: 171 mg (99%); Yellow needle (from CH2Cl2-Hexane); m.p. 144.0–147.0 °C; Rf = 0.21 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.8 Hz, 1H; Ar-H), 7.62 (d, J = 6.9 Hz, 1H; Ar-H), 7.60 (d, J = 7.3 Hz, 1H; Ar-H), 7.39 (s, 1H; Ar-H), 7.36 (d, J = 7.8 Hz, 1H; Ar-H), 7.32–7.16 (m, 5H; Ar-H), 3.83 ppm (s, 3H; N-CH3). 13C NMR (100 MHz, CDCl3): δ = 142.2 (C), 140.5 (C), 137.2 (C), 135.1 (CH), 132.1 (C), 130.3 (C), 126.3 (CH), 124.1 (CH), 123.5 (CH), 122.51 (CH), 122.47 (CH), 121.5 (CH), 120.5 (CH), 120.3 (CH), 109.6 (CH), 97.1 (C), 33.1 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 179.9 ppm. IR (ATR): ν~ = 426, 486, 556, 723, 735, 1236 cm−1. MS (EI, 70 eV): m/z (%) = 343 (14) [M]+, 263 (100), 207 (21), 131 (43), 89 (21), 44 (29). HRMS (ESI): m/z calcd for C17H13NSSe: 342.9934 [M]+; found: 342.9932.

4.3.4. 1,5-Dimethyl-3-phenylselanyl-1H-indole (3ca)

Yield: 133 mg (88%); Colorless plate (from CH2Cl2-Hexane); m.p. 104.0–105.0 °C; Rf = 0.58 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.41 (s, 1H; Ar-H), 7.27–7.20 (m, 4H; Ar-H), 7.14–7.05 (m, 4H; Ar-H), 3.81 (s, 3H; N-CH3), 2.43 ppm (s, 3H; CH3). 13C NMR (100 MHz, CDCl3): δ = 135.83 (C), 135.76 (CH), 134.5 (C), 130.9 (C), 129.8 (C), 128.9 (CH), 128.3 (CH), 125.4 (CH), 124.1 (CH), 120.0 (CH), 109.2 (CH), 95.0 (C), 33.1 (CH3), 21.4 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 206.4 ppm. IR (ATR): ν~ = 424, 457, 731, 793, 1474, 1506 cm−1. MS (EI, 70 eV): m/z (%) = 301 (20) [M]+, 221 (100), 144 (13). HRMS (ESI): m/z calcd for C16H15NSe: 301.0370 [M]+; found: 301.0369.

4.3.5. 5-Chloro-1-methyl-3-phenylselanyl-1H-indole (3da)

Yield: 135 mg (84%); Colorless plate (from CH2Cl2-Hexane); m.p. 132.0–133.5 °C; Rf = 0.54 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.60 (s, 1H; Ar-H), 7.33 (s, 1H; Ar-H), 7.28–7.19 (m, 4H; Ar-H), 7.15–7.08 (m, 3H; Ar-H), 3.82 ppm (s, 3H; N-CH3). 13C NMR (100 MHz, CDCl3): δ = 136.9 (CH), 135.9 (C), 133.7 (C), 131.9 (C), 129.0 (CH), 128.6 (CH), 126.5 (C), 125.7 (CH), 122.8 (CH), 119.9 (CH), 110.7 (CH), 95.7 (C), 33.3 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 209.6 ppm. IR (ATR): ν~ = 422, 457, 689, 733, 795, 1422, 1474 cm−1. MS (EI, 70 eV): m/z (%) = 321 (25) [M]+, 241 (100), 164 (15). HRMS (ESI): m/z calcd for C15H12ClNSe: 320.9823 [M]+; found: 320.9825.

4.3.6. 1-Methyl-3-phenylselanyl-1H-indole-5-carbonitrile (3fa)

Yield: 149 mg (96%); Colorless prism (from CH2Cl2-Hexane); m.p. 198.0–199.5 °C; Rf = 0.34 (CH2Cl2-Hexane, 1:1). 1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 1.4 Hz, 1H; Ar-H), 7.49 (dd, J = 8.7, 1.4 Hz, 1H; Ar-H), 7.45 (s, 1H; Ar-H), 7.41 (d, J = 8.7 Hz, 1H; Ar-H), 7.23–7.20 (m, 2H; Ar-H), 7.17–7.12 (m, 3H; Ar-H), 3.88 ppm (s, 3H; N-CH3). 13C NMR (100 MHz, CDCl3): δ = 139.0 (C), 137.6 (CH), 132.8 (C), 130.5 (C), 129.11 (CH), 129.07 (CH), 126.14 (CH), 126.08 (CH), 125.4 (CH), 120.4 (C), 110.5 (CH), 103.6 (C), 97.9 (C), 33.3 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 212.5 ppm. IR (ATR): ν~ = 461, 474, 631, 692, 741 cm−1. MS (EI, 70 eV): m/z (%) = 312 (17) [M]+, 232 (100), 155 (16). HRMS (ESI): m/z calcd for C16H12N2Se: 312.0166 [M]+; found: 312.0166.

4.3.7. 1,4-Dimethyl-3-phenylselanyl-1H-indole (3ga)

Yield: 138 mg (92%); Colorless plate (from CH2Cl2-Hexane); m.p. 84.0–85.0 °C; Rf = 0.25 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.29 (s, 1H; Ar-H), 7.24–7.18 (m, 4H; Ar-H), 7.15–7.11 (m, 2H; Ar-H), 7.07 (tt, J = 6.9, 1.4 Hz, 1H; Ar-H), 6.89 (d, J = 7.3 Hz, 1H; Ar-H), 3.80 (s, 3H; N-CH3), 2.69 ppm (s, 3H; CH3). 13C NMR (100 MHz, CDCl3): δ = 137.9 (C), 136.8 (CH), 136.4 (C), 132.3 (C), 129.0 (CH), 127.9 (CH), 125.2 (CH), 122.4 (CH), 122.0 (CH), 107.5 (CH), 94.6 (C), 33.1 (CH3), 18.7 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 251.5 ppm. IR (ATR): ν~ = 457, 667, 689, 727, 739, 1474 cm−1. MS (EI, 70 eV): m/z (%) = 301 (33) [M]+, 221 (100), 144 (44). HRMS (ESI): m/z calcd for C16H15NSe: 301.0370 [M]+; found: 301.0369.

4.3.8. 1,6-Dimethyl-3-phenylselanyl-1H-indole (3ha)

Yield: 126 mg (84%); Colorless plate (from CH2Cl2-Hexane); m.p. 86.0–87.5 °C; Rf = 0.45 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 8.2 Hz, 1H; Ar-H), 7.26–7.22 (m, 3H; Ar-H), 7.18 (s, 1H; Ar-H), 7.14–7.06 (m, 3H; Ar-H), 7.01 (d, J = 7.8 Hz, 1H; Ar-H), 3.80 (s, 3H; N-CH3), 2.52 ppm (s, 3H; CH3). 13C NMR (100 MHz, CDCl3): δ = 137.8 (C), 135.1 (CH), 134.3 (C), 132.4 (C), 128.9 (CH), 128.5 (C), 128.4 (CH), 125.4 (CH), 122.1 (CH), 120.1 (CH), 109.5 (CH), 95.6 (C), 32.9 (CH3), 21.8 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 209.3 ppm. IR (ATR): ν~ = 430, 598, 689, 729, 797 cm−1. MS (EI, 70 eV): m/z (%) = 301 (19) [M]+, 221 (100), 144 (17). HRMS (ESI): m/z calcd for C16H15NSe: 301.0370 [M]+; found: 301.0371.

4.3.9. 1,7-Dimethyl-3-phenylselanyl-1H-indole (3ia)

Yield: 113 mg (75%); Colorless plate (from CH2Cl2-Hexane); m.p. 110.0–111.0 °C; Rf = 0.34 (CH2Cl2-Hexane, 1:5). 1H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 7.8 Hz, 1H; Ar-H), 7.24–7.20 (m, 3H; Ar-H), 7.13–7.05 (m, 3H; Ar-H), 7.01 (t, J = 7.3 Hz, 1H; Ar-H), 6.96 (d, J = 6.9 Hz, 1H; Ar-H), 4.08 (s, 3H; N-CH3), 2.79 ppm (s, 3H; CH3). 13C NMR (100 MHz, CDCl3): δ = 137.2 (CH), 136.1 (C), 134.2 (C), 131.8 (C), 128.9 (CH), 128.5 (CH), 125.4 (CH), 125.1 (CH), 121.5 (C), 120.6 (CH), 118.7 (CH), 95.7 (C), 37.0 (CH3), 19.6 ppm (CH3). 77Se NMR (76 MHz, CDCl3): δ = 208.8 ppm. IR (ATR): ν~ = 689, 733, 748, 781, 1450 cm−1. MS (EI, 70 eV): m/z (%) = 301 (18) [M]+, 221 (100), 144 (17). HRMS (ESI): m/z calcd for C16H15NSe: 301.0370 [M]+; found: 301.0370.

4.4. Single-Crystal X-ray Diffraction Experiment of 3aa

A suitable crystal was selected and measured on an XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer. The crystal was kept at 103 K in an N2 cold stream during data collection. Using Olex2 [77], the structure was solved with the SHELXT [78] structure solution program using Intrinsic Phasing and refined with the SHELXL [79] refinement package using Least Squares minimization. Crystal Data for 3aa: C15H13NSe (M = 286.22 g/mol), monoclinic, space group P21/n (no. 14), a = 7.73810(10) Å, b = 9.03610(10) Å, c = 18.1620(2) Å, β = 101.9160(10)°, V = 1242.56(3) Å3, Z = 4, T = 103 K, μ(Cu Kα) = 3.873 mm−1, Dcalc = 1.530 g/cm3, 6253 reflections measured (9.954° ≤ 2Θ ≤ 136.378°), and 2263 unique reflections (Rint = 0.0255 and Rsigma = 0.0218), which were used in all calculations. The final R1 was 0.0243 (I > 2σ(I)), and wR2 was 0.0652 (all data).

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules29133227/s1. The characterization data of known compounds and 1H- and 13C-NMR spectra are available online. The crystal structures have been deposited to the CCDC with the number 2291058, and the CIF files are also provided.

Author Contributions

All authors contributed to the writing and gave approval for the final version of the manuscript. M.M. and S.Y. designed chemical synthesis, analyzed results, and wrote the manuscript. M.M., A.U. and Y.S. performed chemical synthesis experiments and analyzed the results. Y.M. and N.A. analyzed the results and wrote the manuscript. M.M. performed single-crystal X-ray diffraction analysis and wrote the manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by a research grant from the Institute of Pharmaceutical Life Sciences, Aichi Gakuin University.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data that support the findings of this study are available in the manuscript and Supplementary Materials of this article.

Conflicts of Interest

The authors declare no conflicts of interest.

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Molecules 29 03227 g001
Figure 1. Biologically active 3-selanylindoles.
Figure 1. Biologically active 3-selanylindoles.
Molecules 29 03227 g001
Molecules 29 03227 sch001
Scheme 1. Selenation of indoles with diaryl diselenides.
Scheme 1. Selenation of indoles with diaryl diselenides.
Molecules 29 03227 sch001
Molecules 29 03227 g002
Figure 2. ORTEP drawing of 3aa with 50% probability (CCDC 2291058).
Figure 2. ORTEP drawing of 3aa with 50% probability (CCDC 2291058).
Molecules 29 03227 g002
Molecules 29 03227 g003
Figure 3. Substrate scope: reaction of indoles with dichalcogenides [a,b]. [a] 1 (0.5 mmol), 2 (0.25 mmol), BiI3 (0.05 mmol), and DMF (2 mL). [b] Yield of isolated products. [c] 2a (0.5 mmol); 3aa was isolated in a yield of 98%.
Figure 3. Substrate scope: reaction of indoles with dichalcogenides [a,b]. [a] 1 (0.5 mmol), 2 (0.25 mmol), BiI3 (0.05 mmol), and DMF (2 mL). [b] Yield of isolated products. [c] 2a (0.5 mmol); 3aa was isolated in a yield of 98%.
Molecules 29 03227 g003
Molecules 29 03227 sch002
Scheme 2. Possible mechanism.
Scheme 2. Possible mechanism.
Molecules 29 03227 sch002
Table 1. Optimization of the reaction conditions [a].
Table 1. Optimization of the reaction conditions [a].
Molecules 29 03227 i001
EntryCatalystSolventTemp. [°C]Time [h]Yield (%) [b]
1BiCl3DMF1002485
2BiBr3DMF100684
3BiI3DMF100197 (91) [c]
4BiF3DMF1002414
5Bi(OTf)3DMF1002477
6Bi(ONO2)3DMF1002449
7Ph3BiDMF100242
8SbBr3DMF1002477
9SbI3DMF1002474
10AlCl3DMF1002411
11InCl3DMF1002425
12FeCl3DMF1002441
13I2DMF1002420
14BiI3DMSO100289
15BiI3CH3CN802445
16BiI3THF602460
17BiI3MeOH602451
18BiI31,2-DCE80212
19BiI3Dioxane1002419
20BiI3Toluene1002412
21BiI3DMF60889
22 [d]BiI3DMF100194
23 [e]BiI3DMF100249
24 [f]BiI3DMF100894
25 [g]BiI3DMF1002492
26 [h]BiI3DMF100194
27 [i]BiI3DMF100196
[a] Conditions: 1a (0.5 mmol), 2a (0.25 mmol), catalyst (10 mol%), and solvent (2 mL). [b] GC yield using biphenyl as the internal standard. [c] Isolated yield. [d] Under O2. [e] Under argon. [f] BiI3 (5 mol%). [g] BiI3 (1 mol%). [h] TEMPO (0.5 mmol). [i] Diphenylethylene (0.5 mmol).
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MDPI and ACS Style

Matsumura, M.; Umeda, A.; Sumi, Y.; Aiba, N.; Murata, Y.; Yasuike, S. Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles. Molecules 2024, 29, 3227. https://doi.org/10.3390/molecules29133227

AMA Style

Matsumura M, Umeda A, Sumi Y, Aiba N, Murata Y, Yasuike S. Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles. Molecules. 2024; 29(13):3227. https://doi.org/10.3390/molecules29133227

Chicago/Turabian Style

Matsumura, Mio, Airi Umeda, Yuika Sumi, Naoki Aiba, Yuki Murata, and Shuji Yasuike. 2024. "Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles" Molecules 29, no. 13: 3227. https://doi.org/10.3390/molecules29133227

APA Style

Matsumura, M., Umeda, A., Sumi, Y., Aiba, N., Murata, Y., & Yasuike, S. (2024). Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles. Molecules, 29(13), 3227. https://doi.org/10.3390/molecules29133227

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