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Synlett 2015; 26(05): 643-645
DOI: 10.1055/s-0034-1379949
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© Georg Thieme Verlag Stuttgart · New York

A Novel Three-Component Reaction Involving Terminal Alkynes, Elemental Sulfur, and Strained Heterocycles

Alireza Samzadeh-Kermani*
Department of Chemistry, Faculty of Science, University of Zabol, Zabol 054222-26765, Iran   Email: drsamzadeh@gmail.com   Email: arsamzadeh@uoz.ac.ir
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Publication History

Received: 24 September 2014

Accepted after revision: 27 November 2014

Publication Date:
09 February 2015 (online)

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Abstract

An efficient one-pot procedure to synthesize 1,3-oxathiolane-2-alkylidene and 1,3-thiazolidine-2-alkylidene structures is described. Anionic adducts derived from terminal alkynes and elemental sulfur attack strained heterocycles regioselectively to afford the corresponding heterocyclic compounds.

Key words

alkynes - epoxides - heterocycles - multicomponent reaction - sulfur - ring opening

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379949.
  • Supporting Information
 

  • References and Notes

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  • 22 Typical Procedure for the Preparation of 5 and 6 A mixture of NaH (60%w/w in paraffin, 40 mg) in DMF (3 mL) was treated dropwise over 10 min with a solution of the requisite terminal alkyne 1 (1 mmol) in THF (2 mL) at –10 °C. After 30 min elemental sulfur (1.1 mmol) was added, and the mixture was allowed to warm to r.t. Then, 3 or 4 (1 mmol) was added, and the resulting yellow mixture was stirred for 16–22 h at 50 °C. The mixture was quenched with sat. NH4Cl (10 mL) and allowed to stir for 30 min, followed by extraction with CH2Cl2 (3 × 6 mL). The combined organic extracts were dried (Na2SO4), filtered, and concentrated under reduced pressure. The residue was purified by chromatography (silica gel; hexane–EtOAc, 4:1) to give the desired product. 2-Benzylidene-5-methyl-1,3-oxathiolane (5a) Pale yellow oil; yield = 0.17 g (89%). IR (KBr): νmax = 3025, 2967, 1610, 1543, 1326, 1121 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 1.28 (3 H, d, 3 J = 7.2 Hz, Me), 3.26 (H, dd, 2 J = 11.9 Hz, 3 J = 7.1 Hz, CH), 3.41 (H, dd, 2 J = 11.9 Hz, 3 J = 4.9 Hz, CH), 4.82–4.86 (H, m, CH), 5.18 (H, s, CH), 7.12 (H, t, 3 J = 6.9 Hz), 7.20 (2 H, t, 3 J = 6.8 Hz), 7.28 (2 H, d, 3 J = 6.6 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 19.4 (Me), 41.5 (CH2), 78.1 (CH), 123.4 (2 CH), 126.4 (CH), 129.1 (2 CH), 131.7 (CH), 136.3 (C), 163.3 (C). MS: m/z (%) = 192 (2) [M+], 157 (67), 151 (84), 118 (74), 101 (45), 91 (32), 77 (100), 58 (37). Anal. Calcd for C11H12OS (192.28): C, 68.71; H, 6.29; S, 16.68. Found: C, 68.86; H, 6.35; S, 16.73. 2-Benzylidene-5-methyl-5-propyl-1,3-oxathiolane (5b) Pale yellow oil; yield = 0.19 g (83%). IR (KBr): νmax = 3021, 3010, 2945, 1634, 1536, 1325, 1130 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 0.92 (3 H, t, 3 J = 6.2 Hz, Me), 1.32-1.37 (2 H, m,CH2), 1.39 (3 H, s, Me), 1.51 (2 H, t, 3 J = 6.4 Hz, CH2), 3.29 (H, d, 2 J = 11.6 Hz, CH), 3.48 (H, d, 2 J = 11.6 Hz, CH), 5.16 (H, s, CH), 7.13 (H, t, 3 J = 6.7 Hz), 7.23 (2 H, t, 3 J = 6.7 Hz), 7.31 (2 H, d, 3 J = 6.4 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 13.0 (CH2), 14.3 (Me), 23.1 (Me), 39.2 (CH2), 43.1 (CH2), 89.5 (C), 122.1 (2 CH), 125.8 (CH), 130.3 (2 CH), 131.5 (CH), 136.2 (C), 162.9 (C). MS: m/z (%) = 234 (1) [M+], 217 (47), 151 (81), 144 (78), 135 (69), 101 (52), 91 (37), 77 (100), 83 (58). Anal. Calcd for C14H18OS (234.36): C, 71.75; H, 7.74; S, 13.68. Found: C, 71.86; H, 7.89; S, 13.69. 2-Benzylidene-5-phenyl-3-tosylthiazolidine (6a) Pale yellow solid, mp 103–104.5 °C; yield = 0.32 g (78%). IR (KBr): νmax = 3034, 3022, 2957, 1641, 1527, 1512, 1330, 1243, 1137 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 2.23 (3 H, s, Me), 4.29 (H, m, CH), 4.65 (H, dd, 2 J = 11.8 Hz, 3 J = 4.7 Hz, CH), 4.73 (H, dd, 2 J = 11.8 Hz, 3 J = 4.7 Hz, CH), 5.08 (H, s, CH), 7.10–7.31 (10 H, m), 7.35 (2 H, d, 3 J = 6.7 Hz), 7.81 (2 H, d, 3 J = 6.6 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 23.2 (Me), 42.1 (CH2), 69.4 (CH), 113.3 (CH), 125.3 (2 CH), 126.5 (2 CH), 127.0 (CH), 127.4 (2 CH), 128.0 (CH), 128.5 (2 CH), 129.1 (2 CH), 130.5 (2 CH), 136.7 (C), 137.0 (C), 140.2 (C), 143.9 (C), 155.3 (C). MS: m/z (%) = 407 (1) [M+], 375 (37), 304 (85), 272 (61), 220 (80), 155 (73), 103 (41), 77 (100). Anal. Calcd for C23H21NO2S2 (407.55): C, 67.78; H, 5.19; N, 3.44; S, 15.74. Found: C, 67.89; H, 5.30; N, 3.52; S, 15.78. 4-Benzyl-2-butylidene-3-tosylthiazolidine (6b) Pale yellow solid, mp 89–91 °C; yield = 0.27 g (69%). IR (KBr): νmax = 3047, 3021, 2952, 1647, 1527, 1510, 1326, 1310, 1236, 1127 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 0.91 (3 H, t, 3 J = 6.1 Hz, Me), 1.29–1.34 (2 H, m, CH2), 2.11–2.14 (2 H, m, CH2), 2.25 (3 H, s, Me), 3.21 (H, dd, 2 J = 11.9 Hz, 3 J = 7.1 Hz, CH), 3.32 (H, dd, 2 J = 11.9 Hz, 3 J = 4.9 Hz, CH), 3.53 (2 H, m, CH2), 4.59 (H, t, 3 J = 6.3 Hz, CH), 5.13–5.19 (H, m, CH), 7.11–7.29 (5 H, m), 7.36 (2 H, d, 3 J = 6.4 Hz, 2 CH), 7.82 (2 H, d, 3 J = 6.5 Hz, 2 CH). 13C NMR (125.7 MHz, CDCl3): δ = 13.2 (Me), 23.2 (CH2), 24.2 (Me), 27.2 (CH2), 42.7 (CH2), 47.0 (CH2), 68.9 (CH), 108.4 (CH), 126.1 (CH), 127.4 (2 CH), 129.1 (2 CH), 129.8 (2 CH), 131.4 (2 CH), 135.9 (C), 139.1 (C), 143.0 (C), 157.2 (C). MS: m/z (%) = 387 (1) [M+], 354 (40), 270 (86), 238 (72), 200 (68), 155 (59), 117 (53), 77 (100). Anal. Calcd for C21H25NO2S2 (387.56): C, 65.08; H, 6.50; N, 3.61; S, 16.55. Found: C, 65.19; H, 6.64; N, 3.70; S, 16.62.