Solvent Effect on Base-Free Synthesis 4-Substituted 2-Oxazolines via Intramolecular Cyclodemesylation

Erdin Dalkılıç; Yakup Güneş

doi:10.1055/s-0042-1751491

Synlett, Table of Contents

Synlett 2024; 35(07): 735-740
DOI: 10.1055/s-0042-1751491

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Solvent Effect on Base-Free Synthesis 4-Substituted 2-Oxazolines via Intramolecular Cyclodemesylation

Erdin Dalkılıç∗

^aFood and Agriculture Vocational School, Çankırı Karatekin University, Çankırı, 18100, Turkey

^bCentral Research Laboratory (ÇANKAM), Çankırı Karatekin University, Çankırı, 18100, Turkey

,

Yakup Güneş ∗

^cFaculty of Education, Department of Basic Education, Siirt University, Siirt, 56100, Turkey

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Abstract

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Abstract

In this present study, the solvent effect was examined for the synthesis of 2-oxazolines via intramolecular cyclodemesylation. To determine the solvent effect, aprotic/protic polar and nonpolar solvents were screened and polar protic solvents met the best result. The remarkable feature of this synthesis is that cyclization takes place in the absence of any base or reagent, in high yields (89–96%). As a result, a series of 4-substituted chiral 2-oxazolines were successfully synthesized through a four-step process, with overall yields reaching between 79% and 88% in a greener approach.

Key words

solvent effect - green chemistry - heterocycles - intramolecular cyclization - 2-oxazoline

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References and Notes
1 Inahashi Y, Iwatsuki M, Ishiyama A, Namatame M, Nishihara-Tsukashima A, Matsumoto A, Hirose T, Sunazuka T, Yamada H, Otoguro K, Takahashi Y, O’mura S, Shiomi K. J. Antibiot. 2011; 64: 303
2 Shaaban KA, Saunders MA, Zhang Y, Tran T, Elshahawi SI, Ponomareva LV, Wang X, Zhang J, Copley GC, Sunkara M, Kharel MK, Morris AJ, Hower JC, Tremblay MS, Prendergast MA, Thorson JS. J. Nat. Prod. 2017; 80: 2
3 Kamińska K, Mular A, Olshvang E, Nolte NM, Kozłowski H, Wojaczyńska E, Gumienna-Kontecka E. RSC Adv. 2022; 12: 25284
4 Tyler AR, Mosaei H, Morton S, Waddell PG, Wills C, McFarlane W, Gray J, Goodfellow M, Errington J, Allenby N, Zenkin N, Hall MJ. J. Nat. Prod. 2017; 80: 1558
5 Nelson KM, Salomon CE, Aldrich CC. J. Nat. Prod. 2012; 75: 1037
6 Crosignani S, Swinnen D. J. Comb. Chem. 2005; 7: 688
7 Maftei CV, Fodor E, Jones PG, Daniliuc CG, Franz MH, Kelter G, Fiebig HH, Tamm M, Neda I. Rev. Roum. Chim. 2015; 60: 75
8 Chen S, Zhang Y, Liu Y, Wang Q. J. Agric. Food. Chem. 2021; 69: 3601
9 Chang W, Nie J, Yan Z, Wang Y, Farooq S. J. Agric. Food. Chem. 2019; 67: 6708
10 Kline T, Andersen NH, Harwood EA, Bowman J, Malanda A, Endsley S, Erwin AL, Doyle M, Fong S, Harris AL, Mendelsohn B, Mdluli K, Raetz CR. H, Stover CK, Witte PR, Yabannavar A, Zhu S. J. Med. Chem. 2002; 45: 3112
11 Pirrung MC, Tumey LN, McClerren AL, Raetz CR. H. J. Am. Chem. Soc. 2003; 125: 1575
12 Ghosh AK, Mathivanan P, Cappiello J. Tetrahedron: Asymmetry 1998; 9: 1
13 Connon R, Roche B, Rokade BV, Guiry P. J. Chem. Rev. 2021; 121: 6373
14 Helmchen G, Pfaltz A. Acc. Chem. Res. 2000; 33: 336
15 Meyers AI. J. Org. Chem. 2005; 70: 6137
16 Shrestha B, Rose BT, Olen CL, Roth A, Kwong AC, Wang Y, Denmark SE. J. Org. Chem. 2021; 86: 3490
17 Gant TG, Meyers AI. Tetrahedron 1994; 50: 2297
18 Chen K, Li ZW, Shen PX, Zhao HW, Shi ZJ. Chem. Eur. J. 2015; 21: 7389
19 Luxenhofer R, Han Y, Schulz A, Tong J, He Z, Kabanov AV, Jordan R. Macromol. Rapid Commun. 2012; 33: 1613
20 Sedlacek O, Lava K, Verbraeken B, Kasmi S, De Geest BG, Hoogenboom R. J. Am. Chem. Soc. 2019; 141: 9617
21 Wu YC. M, Swager TM. J. Am. Chem. Soc. 2019; 141: 12498
22 Sahn M, Weber C, Schubert US. Polym. Rev. 2019; 59: 240
23 Li X, Taechalertpaisarn J, Xin D, Burgess K. Org. Lett. 2015; 17: 632
24 Phillips AJ, Uto Y, Wipf P, Reno MJ, Williams DR. Org. Lett. 2000; 2: 1165
25 Gilbert A, Bertrand X, Paquin JF. Org. Lett. 2018; 20: 7257
26 Deng QH, Chen JR, Wei Q, Zhao QQ, Lu LQ, Xiao W. J. Chem. Commun. 2015; 51: 3537
27 Meyers AI. J. Heterocycl. Chem. 1998; 35: 991
28 Kamata K, Agata I, Meyers AI. J. Org. Chem. 1998; 63: 3113
29 Deng H, Wang J, He W, Ye Y, Bai R, Zhang X, Ye X.-Y, Xie T, Hui Z. Org. Biomol. Chem. 2023; 21: 2312
30 Pouambeka TW, Enoua GC, Obaya NN, Loumouamou BW, Makomo H, N’goka V. Mod. Chem. 2022; 10: 56
31 Rajaram S, Sigman MS. Org. Lett. 2002; 4: 3399
32 Crosignani S, Young AC, Linclau B. Tetrahedron Lett. 2004; 45: 9611
33 Khapli S, Dey And S, Mal D. J. Indian Inst. Sci. 2001; 81: 461
34 Wipf P, Miller CP. Tetrahedron Lett. 1992; 33: 907
35 Movahed FS, Foo SW, Mori S, Ogawa S, Saito S. J. Org. Chem. 2022; 87: 243
36 Gao WC, Hu F, Huo YM, Chang HH, Li X, Wei WL. Org. Lett. 2015; 17: 3914
37 Liu GQ, Yang CH, Li YM. J. Org. Chem. 2015; 80: 11339
38 Chavan SS, Rupanawar BD, Kamble RB, Shelke AM, Suryavanshi G. Org. Chem. Front. 2018; 5: 544
39 Yang T, Huang C, Jia J, Wu F, Ni F. Molecules 2022; 27: 9042
40 Inagaki T, Phong LT, Furuta A, Ito JI, Nishiyama H. Chem. Eur. J. 2010; 16: 3090
41 Treat A, Henri V, Liu J, Shen J, Gil-Silva M, Morales A, Rade A, Tidgewell KJ, Kolber B, Shen Y. ACS Omega 2022; 7: 2929
42 Dagorne S, Bellemin-Laponnaz S, Welter R. Organometallics 2004; 23: 3053
43 Zhou Y, Wang L, Yuan G, Liu S, Sun X, Yuan C, Yang Y, Bian Q, Wang M, Zhong J. Org Lett. 2020; 22: 4532
44 Harada S, Kobayashi M, Kono M, Nemoto T. ACS Catal. 2020; 10: 13296
45 Clayden J, Clayton J, Harvey RA, Karlubíková O. Synlett 2009; 2836
46 Hall JD, Duncan-Gould NW, Siddiqi NA, Kelly JN, Hoeferlin LA, Morrison SJ, Wyatt JK. Bioorg. Med. Chem. 2005; 13: 1409
47 Thanigaimalai P, Konno S, Yamamoto T, Koiwai Y, Taguchi A, Takayama K, Yakushiji F, Akaji K, Chen SE, Naser-Tavakolian A, Schön A, Freire E, Hayashi Y. Eur. J. Med. Chem. 2013; 68: 372
48 Surivet JP, Zumbrunn C, Rueedi G, Hubschwerlen C, Bur D, Bruyère T, Locher H, Ritz D, Keck W, Seiler P, Kohl C, Gauvin JC, Mirre A, Kaegi V, Dos Santos M, Gaertner M, Delers J, Enderlin-Paput M, Boehme M. J. Med. Chem. 2013; 56: 7396
49 Or YS, Ying L, Wang C, Long J, Qiu Y.-L. WO2009/003009A1, 2009
50 Zhou J, Tang Y. Chem. Soc. Rev. 2005; 34: 664
51 Krout MR, Mohr JT, Stoltz BM. Org. Synth. 2009; 86: 181
52 Wang Y, Hämäläinen A, Tois J, Franzén R. Tetrahedron: Asymmetry 2010; 21: 2376
53 Yang D, Zhu Y, Yang N, Jiang Q, Liu R. Adv. Synth. Catal. 2016; 358: 1731
54 Hossain SU, Sengupta S, Bhattacharya S. Bioorg. Med. Chem. 2005; 13: 5750
55 Sk UH, Prakasha Gowda AS, Crampsie MA, Yun JK, Spratt TE, Amin S, Sharma AK. Eur. J. Med. Chem. 2011; 46: 3331
56 (–)-(S)-2-(Furan-2-yl)-4-isobutyl-4,5-dihydrooxazole (1f) – General Procedure A solution of 1c (211 mg, 0.73 mmol, 1.0 equiv) in EtOH (10 mL) was stirred for 2 h at 45 °C. After stirring for 2 h, to the mixture was added NEt₃ (148 mg, 1.47 mmol, 0.20 mL 2.0 equiv) and stirred for 5 min. Then, the mixture was concentrated and EtOAc (15 mL) was added. The organic layers were washed with water (15 mL) and brine (15 mL). The organic layer was dried over Na₂SO₄, filtered, and concentrated in vacuo to give the crude product. The residues were purified by column chromatography (PE/EtOAc = 8:2) to give a colorless liquid; yield 135 mg (96%). [α]_D ²⁰ –70 (c 1.00, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 7.51 (dd, J = 1.9, 0.8 Hz, 1 H), 6.92 (dd, J = 3.5, 0.8 Hz, 1 H), 6.46 (dd, J = 3.5, 1.9 Hz, 1 H), 4.47 (dd, J = 9.3, 8.0 Hz, 1 H), 4.31 (dq, J = 9.3, 7.3 Hz, 1 H), 3.93 (t, J = 8.0 Hz, 1 H), 1.84 (dt, J = 13.6, 6.8 Hz, 1 H), 1.70 (dt, J = 13.6, 6.8 Hz, 1 H), 1.35 (dt, J = 13.6, 7.3 Hz, 1 H), 0.96 (d, J = 6.7 Hz, 3 H), 0.94 (d, J = 6.7 Hz, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 155.85, 145.24, 143.23, 114.27, 111.60, 73.38, 65.21, 45.57, 25.53, 22.94, 22.79. HRMS: m/z calcd for C₁₁H₁₆NO₂: 194.1181 [M + H]⁺; found: 194.1185.
57 Brunner H, Haßler B. Z. Naturforsch., B: J. Chem. Sci. 1998; 53: 476
58 Allen JV, Dawson GJ, Frost CG, Williams JM. J, Coote SJ. Tetrahedron 1994; 50: 799
59 Lu P, Ji CL, Lu Z. Asian J. Org. Chem. 2018; 7: 542

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