Direct Access to S-Heterocycles by Scandium(III) Triflate Catalyzed Cyclization of Aromatic Thiols and Diols

Maki Minakawa; Keisuke Minami; Yuya Sato

doi:10.1055/s-0040-1720350

Synlett, Table of Contents

Synlett 2021; 32(18): 1869-1873
DOI: 10.1055/s-0040-1720350

letter

Direct Access to S-Heterocycles by Scandium(III) Triflate Catalyzed Cyclization of Aromatic Thiols and Diols

Maki Minakawa∗

,

Keisuke Minami

,

Yuya Sato

Abstract

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Abstract

A simple and environmentally friendly method to prepare S-heterocycles by cyclization of aromatic thiols and diols with H₂O as a byproduct is described. The Sc(OTf)₃-catalyzed dehydrative cyclizations of aromatic thiols and diols provided the corresponding thiopyran and thiophene derivatives. Control experiments were also performed to obtain insights into the reaction pathway

Key words

S-heterocycles - diols - thiols - scandium triflate - cyclization - C–S bond formation

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References

References and Notes

1a Dunbar KL, Scharf DH, Litomska A, Hertweck C. Chem. Rev. 2017; 117: 5521
1b Feng M, Tang D, Liang SH, Jiang X. Curr. Top. Med. Chem. (Sharjah, United Arab Emirates) 2016; 16: 1200
1c Chauhan P, Mahajan S, Enders D. Chem. Rev. 2014; 114: 8807
1d Gangjee A, Talreja T, McGuire JJ, Kisliuk RL, Queener SF. J. Med. Chem. 2007; 50: 3046

2a Beletskaya IP, Ananikov VP. Chem. Rev. 2011; 111: 1596
2b Tsumi K, Fujimoto K, Yabukami T, Kawase T, Morimoto T, Kakiuchi K. Eur. J. Org. Chem. 2004; 504
2c Tanaka K, Hori T, Osaka T, Noguchi K, Hirano M. Org. Lett. 2007; 9: 4881
2d Yatsumonji Y, Ishida Y, Tsubouchi A, Takeda T. Org. Lett. 2007; 9: 4603
2e Delcaillau T, Bismuto A, Lian Z, Morandi B. Angew. Chem. Int. Ed. 2020; 59: 2110
2f Hori T, Shibata Y, Tanaka K. Tetrahedron: Asymmetry 2010; 21: 1303
2g Schlatzer T, Schröder H, Trobe M, Lembacher-F C, Stangl S, Schlögl C, Weber H, Breinbauer R. Adv. Synth. Catal. 2020; 362: 331
2h Schlatzer T, Kriegesmann J, Schröder H, Trobe M, Lembacher-F C, Santner S, Kravchuk AV, Becker CF. W, Breinbauer R. J. Am. Chem. Soc. 2019; 141: 14931

3a Kondo T, Mitsudo T.-a. Chem. Rev. 2000; 100: 3205
3b Xi H, Ma E, Li Z. Tetrahedron 2016; 72: 4111
3c Di Giuseppe A, Castarlenas R, Peŕez-Torrente JJ, Crucianelli M, Polo V, Sancho R, Lahoz FJ, Oro LA. J. Am. Chem. Soc. 2012; 134: 8171
3d Weiss CJ, Marks TJ. J. Am. Chem. Soc. 2010; 132: 10533
3e Hong DJ, Kim DW, Chi DY. Tetrahedron Lett. 2010; 51: 54
3f Nakazawa T, Shibazaki M, Itabashi K. Nippon Kagaku Kaishi 1987; 1: 45
3g Nakazawa T, Takagaki N, Shimizu M, Itabashi K. Nippon Kagaku Kaishi 1985; 4: 725
3h Still IW. J, Arora PC, Hasan SK, Kutney GW, Lo LY. T, Turnbull K. Can. J. Chem. 1981; 59: 199
3i Clark PD, McKinnin DM. Can. J. Chem. 1981; 59: 227

4a Rungtaweevoranit B, Butsuri A, Wongma K, Sadorn K, Neranon K, Nerungsi C, Thongpanchang T. Tetrahedron Lett. 2012; 53: 1816
4b Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 8652 ; corrigendum: Angew. Chem. Int. Ed. 2014, 53, 348
4c Zaitsev AB, Caldwell HF, Pregosin PS, Veiros LF. Chem. Eur. J. 2009; 15: 6468
4d Carma A, Navas J, Ródenas T, Sabater MJ. Chem. Eur. J. 2013; 19: 17464
4e Firouzabadi H, Iranpoor N, Jafarpour M. Tetrahedron Lett. 2006; 47: 93
4f Sorribes I, Corma A. Chem. Sci. 2019; 10: 3130
4g Adude R, Goswami SV, Pagare BY, Bhusare SR. Chem. Sci. Trans. 2013; 2: 282
4h Han X, Wu J. Org. Lett. 2010; 12: 5780

5a Ilardi EA, Vitaku E, Njardarson JT. J. Med. Chem. 2014; 57: 2832
5b Przybylski P, Pyta-Klich K, Pyta K, Janas A. Tetrahedron 2018; 74: 6335
5c Yoneya T, Taniguchi K, Nakamura R, Tsunenari T, Ohizumi I, Kanbe Y, Morikawa K, Kaiho S.-i, Yamada-Okabe H. Anticancer Res. 2010; 30: 873
5d Sadorn K, Sinananwanich W, Areephong J, Nerungsi C, Wongma C, Pakawatchai C, Thongpanchang T. Tetrahedron Lett. 2008; 49: 4519
5e Wu D, Pisula W, Haberecht MC, Feng X, Müllen K. Org. Lett. 2009; 11: 5686
5f Franzmann P, Beil SB, Schollmeyer D, Waldvogel SR. Chem. Eur. J. 2019; 25: 1936

6a Robillard B, Hughes L, Slaby M, Lindsay DA, Ingold KU. J. Org. Chem. 1986; 51: 1700
6b Waugh KM, Berlin KD, Ford WT, Holt EM, Carrol JP, Schomber PR, Thompson MD, Schiff LJ. J. Med. Chem. 1985; 28: 116
6c Truce WE, Milionis JP. J. Am. Chem. Soc. 1952; 74: 974
6d Bordwell FG, McKellin WH. J. Am. Chem. Soc. 1951; 73: 2251

7a Nishino K, Ogiwara Y, Sakai N. Chem. Eur. J. 2018; 24: 10971
7b You W, Yan X, Liao Q, Xi C. Org. Lett. 2010; 12: 3930
7c Qiao Z, Liu H, Xiao Y, Fu Y, Wei J, Li Y, Jiang X. Org. Lett. 2013; 15: 2594
7d Castanheiro T, Donnard M, Gulea M, Suffert J. Org. Lett. 2014; 16: 3060

8 Minakawa M, Watanabe K, Toyoda S, Uozumi Y. Synlett 2018; 29: 2385
9 Di-2-naphthyl disulfide was obtained in a quantitative yield (see also Scheme 4a).
10 Under similar reaction conditions at 150 °C, 3aa was obtained in an isolated yield of 55%. In addition, when the reaction was performed with 10 mol% of Sc(OTf)₃, 3aa was obtained in 66% yield.
11 Di-2-naphthyl disulfide was obtained in a quantitative yield.
12 3ja: HRMS: m/z calcd for C₁₀H₉F₃S: 218.03771; found: 218.03755. 4ja: HRMS: m/z calcd for C₁₀H₇F₃S: 216.02206; found: 216.02411.
13 3,3-Dimethyl-2,3-dihydro-1H-naphtho[2,1-b]thiopyran (3af) and 1,1-Dimethyl-2,3-dihydro-1H-naphtho[2,1-b]thiopyran (3′af); Typical Procedure A vial was charged with naphthalene-2-thiol (1a; 16.0 mg, 0.1 mmol), Sc(OTf)₃ (2.5 mg, 5.0 mol%), and 3-methylbutane-1,3-diol (2f; 0.1 mL), and the mixture was stirred at 165 °C for 16 h. The mixture was then diluted with EtOAc (1.0 mL) and H₂O (1.0 mL) was added. The mixture was stirred well, then the organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 1.0 mL). The organic layers were combined, dried (Na₂SO₄), and concentrated under reduced pressure. The residue was purified by PTLC (Wakogel B-5F, hexane–EtOAc, 50:1) to give a mixture of 3af and 3′af as a white oil; yield: 18.9 mg (83%). 3af Pale-yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 1.45 (s, 6 H), 2.09 (t, J = 6.8 Hz, 2 H), 3.29 (t, J = 6.5 Hz, 2 H), 7.13 (d, J = 8.5 Hz, 1 H), 7.39 (t, J = 7.4 Hz, 1 H), 7.50 (t, J = 7.1 Hz, 1 H), 7.57 (d, J = 8.5 Hz, 1 H), 7.75 (d, J = 8.5 Hz, 1 H), 7.93 (d, J = 8.5 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 23.3, 29.2 (2 C), 37.6, 41.5, 121.8, 124.3, 125.3, 126.1, 126.4, 126.5, 128.6, 130.9, 131.2, 132.8. HRMS (GC-MS): m/z [M⁺] calcd for C₁₅H₁₆S: 228.0973; found: 228.1013. 3′af ¹H NMR: δ = 1.69 (s, 6 H), 2.18–2.20 (m, 2 H), 3.00–3.01 (m, 2 H), 7.13 (d, J = 8.4 Hz, 1 H), 7.33 (t, J = 7.6 Hz, 1 H), 7.41–7.44 (m, 1 H), 7.49 (d, J = 8.4 Hz, 1 H), 7.71–7.73 (m, 1 H), 8.30 (d, J = 7.8 Hz, 1 H). HRMS (GC-MS): m/z [M⁺] calcd for C₁₅H₁₆S: 228.09973; found: 228.1010.
14 Under N₂, naphthalene-2-thiol and di-2-naphthyl disulfide were recovered in yields of 28% and 13%, respectively. Under O₂, naphthalene-2-thiol and di-2-naphthyl disulfide were not detected in a ¹H NMR analysis (the ¹H NMR spectra were messy).
15 Naphthalene-2-thiol was not detected, and di-2-naphthyl disulfide was obtained (TEMPO: 29%, DPPH: 14%).
16 Di-2-naphthyl disulfide was recovered (TEMPO: 58%, DPPH: 41%).
17 Under similar reaction conditions without the Sc(OTf)₃ catalyst, the cyclized products 3af and 3′af were not detected in the ¹H NMR analysis, and only the starting material 7a was recovered.

18a Dénès F, Pichowicz M, Povie G, Renaud P. Chem. Rev. 2014; 114: 2587
18b Kwart H, Hackett CM. J. Am. Chem. Soc. 1962; 84: 1754
18c Hui Z, Jiang S, Qi X, Ye X.-Y, Xie T. Tetrahedron Lett. 2020; 61: 151995
18d Morin L, Lebaud J, Paquer D, Chaussin R, Barillier D. Phosphorus Sulfur Relat. Elem. 1979; 7: 69
18e Leleti RR, Hu B, Prashad M, Repič O. Tetrahedron Lett. 2007; 48: 8505
18f Chen CH, Reynolds GA, Zumbulyadis N, Van Allan JA. J. Heterocycl. Chem. 1978; 15: 289

19 Kwart H, Johnson N. J. Am. Chem. Soc. 1970; 92: 6064
20 Vu MD, Foo CQ, Sadeer A, Shand SS, Li Y, Pullarkat SA. ACS Omega 2018; 3: 8945
21 Youn SW, Eom JI. J. Org. Chem. 2006; 71: 6705

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