An Efficient Access to Selenazoline-4-Carboxylate Derivatives Incorporating Cyclopropyl Groups

Xian Huang; Wan-Li Chen; Hong-Wei Zhou

doi:10.1055/s-2003-44969

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Synlett 2004(2): 0329-0331
DOI: 10.1055/s-2003-44969

LETTER

An Efficient Access to Selenazoline-4-Carboxylate Derivatives Incorporating Cyclopropyl Groups

Xian Huang*^a,b, Wan-Li Chen^a, Hong-Wei Zhou^a
^a Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou, P. R. China
Fax: +86(571)88807077; e-Mail: huangx@mail.hz.zj.cn;
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, P. R. China

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Publication History

Received 17 September 2003
Publication Date:
04 December 2003 (online)

Abstract
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Abstract

5-Spirocyclopropane-annulated selenazoline-4-carboxylates were synthesized in good yield via Michael addition of selenoamide to 2-bromo-2-cyclopropylideneacetate followed by an intramolecular substitution under basic conditions (NaHCO₃, MeCN).

Key words

Michael addition - selenoamide - selenium heterocycles

References

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10

Typical Procedure for the Synthesis of 4: A solution of the respective ethyl-2-bromo-2-cyclopropylideneacetate [2] (1) (0.5 mmol), selenoamide [13] 2 (0.5mmol), and NaHCO₃ (1.00 g, 11.9 mmol) in freshly distilled MeCN (10 mL) was heated under reflux for 1-2 h. After filtration, the solvent was evaporated in vacuo. The residue was subjected to preparative TLC (eluent: petroleum ether-Et₂O, 3:1) to afford the product 4.
4a: IR (film): 3062, 2981, 1747, 1729, 1255, 1180 cm^-1. ¹H NMR (CDCl₃): δ = 7.76-7.78 (m, 2 H), 7.46-7.48 (m, 1 H), 7.39-7.43 (m, 2 H), 4.83 (s, 1 H), 4.20-4.25 (q, J = 7.1 Hz, 2 H), 1.27-1.31 (t, J = 7.1 Hz, 3 H), 1.13-1.17 (m, 4 H). ¹³C NMR (CDCl₃): δ = 171.27, 168.44, 135.60, 131.60, 128.96, 128.60, 86.01, 61.34, 32.13, 16.63, 14.30, 9.36. MS (EI): m/z: 309 (4.64) [M⁺(Se⁸⁰)], 236 (100). Anal. Calcd for C₁₄H₁₅NO₂Se: C, 54.55, H, 4.91, N, 4.54. Found: C, 54.70; H, 4.98; N, 4.50. 4b: IR (film): 3067, 2981, 1747, 1730, 1181, 1092 cm^-1. ¹H NMR (CDCl₃): δ = 7.69-7.72 (d, J = 8.8 Hz, 2 H), 7.38-7.40 (d, J = 8.8 Hz, 2 H), 4.82 (s, 1 H), 4.21-4.26 (q, J = 7.1 Hz, 2 H), 1.31-1.28 (t, J = 7.1 Hz, 3 H), 1.14-1.18 (m, 4 H). ¹³C NMR (CDCl₃): δ = 169.93, 168.27, 137.68, 134.08, 130.16, 128.83, 85.97, 61.41, 32.57, 16.57, 14.29, 9.36. MS (EI): m/z = 343 (5.43) [M⁺(Se⁸⁰,Cl³⁵)], 270 (100). Anal. Calcd for C₁₄H₁₄ClNO₂Se: C, 49.07; H, 4.12; N, 4.09. Found: C, 48.81; H, 4.20; N, 4.20.
4c: IR (film): 3065, 2980, 1745, 1729, 1179, 1096 cm^-1. ¹H NMR (CDCl₃): δ = 7.63-7.65 (d, J = 8.4 Hz, 2 H), 7.54-7.56 (d, J = 8.4 Hz, 2 H), 4.81 (s, 1 H), 4.20-4.26 (q, J = 7.1 Hz, 2 H), 1.28-1.31 (t, J = 7.1 Hz, 3 H), 1.14-1.17 (m, 4 H). ¹³C NMR (CDCl₃): δ = 170.05, 168.23, 134.54, 131.80, 130.33, 126.16, 86.02, 61.41, 32.57, 16.57, 14.27, 9.37. MS (EI): m/z = 387 (4.23) [M⁺(Se⁸⁰,Br⁷⁹)], 97 (100), 314 (23.72). Anal. Calcd for C₁₄H₁₄BrNO₂Se: C, 43.43; H, 3.65; N, 3.62. Found: C, 43.55; H, 3.72; N, 3.60.
4d: IR (film): 3065, 2891, 1746,1730, 1245, 1281 cm^-1. ¹H NMR (CDCl₃): δ = 7.96-7.97 (t, J = 1.7 Hz, 1 H), 7.59-7.66 (m, 2 H), 7.27-7.31 (t, J = 7.8 Hz, 1 H), 4.83 (s, 1 H), 4.19-4.25 (q, J = 7.1 Hz, 2 H), 1.28-1.32 (t, J = 7.1 Hz, 3 H) 1.14-1.18 (m, 4 H). ¹³C NMR (CDCl₃): δ = 169.73, 168.17, 137.45, 134.44, 131.39, 130.07, 127.81, 122.75, 85.96, 61.45, 32.57, 16.55, 14.28, 9.39. MS (EI): m/z = 387 (4.23) [M⁺(Se⁸⁰,Br⁷⁹)], 314 (100). Anal. Calcd for C₁₄H₁₄BrNO₂Se: C, 43.43; H, 3.65; N, 3.62. Found: C, 43.23; H, 3.73; N, 3.60.
4e: IR (film): 3063, 2980, 1747, 1728, 1255, 1179 cm^-1. ¹H NMR (CDCl₃): δ = 7.65-7.67 (d, J = 8.1 Hz, 2 H), 7.20-7.22 (d, J = 8.1 Hz, 2 H), 4.81 (s, 1 H), 4.17-4.23 (q, J = 7.1 Hz, 2 H), 2.39 (s, 3 H), 1.27-1.31 (t, J = 7.1 Hz, 3 H), 1.13-1.17 (m, 4 H). ¹³C NMR (CDCl₃): δ = 171.05, 168.57, 142.07, 133.03, 129.26, 128.94, 86.00, 61.28, 32.00, 21.52, 16.62, 14.28, 9.34. MS (EI): m/z = 323 (3.28) [M⁺(Se⁸⁰)], 250(100). Anal. Calcd for C₁₅H₁₇NO₂Se: C, 55.91; H, 5.32; N, 4.35. Found: C, 55.79; H, 5.40; N, 4.41.
4f: IR (film): 3065, 2981, 1746,1729, 1265, 1181 cm^-1. ¹H NMR (CDCl₃): δ = 7.64 (s, 1 H), 7.55-7.56 (m, 1 H), 7.29-7.30 (m, 2 H), 4.83 (s, 1 H), 4.22-4.25 (q, J = 7.1 Hz, 2 H), 2.39 (s, 3 H), 1.28-1.31 (t, J = 7.1 Hz, 3 H), 1.14-1.17 (m, 4 H). ¹³C NMR (CDCl₃): δ = 171.40, 168.25, 138.49, 135.14, 132.71, 129.32, 128.56, 126.54, 85.38, 61.43, 31.89, 21.22, 16.81, 14.29, 9.23. MS (EI): m/z = 323 (3.83) [M⁺(Se⁸⁰)], 250 (100).; Anal. Calcd for C₁₅H₁₇NO₂Se: C, 55.91; H, 5.32; N, 4.35. Found: C, 56.08; H, 5.21; N, 4.42.
4g: IR (film): 3063, 2982, 1732, 1253, 1182 cm^-1. ¹H NMR (CDCl₃): δ = 7.75-7.79 (m, 2 H), 7.08-7.12 (m, 2 H), 4.81 (s, 1 H), 4.20-4.24 (q, J = 7.1 Hz, 2 H), 1.28-1.32 (t, J = 7.1 Hz, 3 H), 1.14-1.18 (m, 4 H). ¹³C NMR (CDCl₃): δ = 171.27, 168.36, 164.73 (d, J = 250.9 Hz), 131.96 (d, J = 3.1 Hz), 131.03 (d, J = 8.7 Hz), 115.66 (d, J = 22 Hz), 85.96, 61.37, 32.58, 16.57, 14.27, 9.32; MS (EI): m/z = 327 (2.60) [M⁺(Se⁸⁰)], 254 (100). Anal. Calcd for C₁₄H₁₄FNO₂Se: C, 51.54; H, 4.33; N, 4.29. Found: C, 51.69; H, 4.40; N, 4.13.
4h: IR (film): 3064, 2981, 1747, 1727, 1254, 1037 cm^-1. ¹H NMR (CDCl₃): δ = 7.35 (s, 1 H), 7.21-7.24 (m, 1 H), 6.80-6.82 (d, J = 8.0 Hz, 1 H), 6.02 (s, 2 H), 4.78 (s, 1 H), 4.18-4.25 (q, J = 7.1 Hz, 2 H), 1.27-1.31 (t, J = 7.1 Hz, 3 H), 1.13-1.16 (m, 4 H). ¹³C NMR (CDCl₃): δ = 170.02, 168.56, 150.50, 147.98, 130.08, 125.00, 108.17, 108.04, 101.73, 85.81, 61.30, 32.22, 16.60, 14.29, 9.27. MS (EI): m/z = 353 (1.03) [M⁺(Se⁸⁰)], 84 (100), 280 (17.15). Anal. Calcd for C₁₅H₁₅NO₄Se: C, 51.15; H, 4.29; N, 3.98 Found: C, 51.00; H, 4.38; N, 4.08.
4i: IR (film): 3065, 2980, 1746, 1728, 1252, 1105 cm^-1. ¹H NMR (CDCl₃): δ = 7.29-7.40 (m, 5 H), 4.81 (s, 1 H), 4.30 (s, 2 H), 4.20-4.25 (q, J = 7.1 Hz, 2 H), 1.27-1.31 (t, J = 7.1 Hz, 3 H), 1.14-1.18 (m, 4 H). ¹³C NMR (CDCl₃): δ = 171.11, 168.40, 135.35, 129.10, 128.45, 127.78, 85.98, 61.29, 43.10, 32.04, 16.53, 14.29, 9.35. MS (EI): m/z = 323 (3.60) [M⁺(Se⁸⁰)]. Anal. Calcd for C₁₅H₁₇NO₂Se: C, 55.91; H, 5.32; N, 4.35; Found: C, 55.80; H, 5.40; N, 4.20.

12

Typical procedure: A solution of 4a (171 mg, 0.5 mmol) with CuBr₂ (450 mg, 2 mmol) in MeCN (10 mL) was stirred under reflux and was monitored by TLC. After the reaction was completed, the mixture was diluted with 20 mL of sat. NH₄Cl and then extracted with Et₂O (3 ×). The Et₂O phases were combined and dried over MgSO_4. After evaporation, the residue was subjected to preparative TLC (eluent: petroleum ether-Et₂O, 3:1) to afford 5a 192mg (82%). IR(film): 3061, 2980, 1735 cm^-1. ¹H NMR (CDCl₃): δ = 7.99-8.01 (m, 2 H), 7.52-7.56 (m, 1 H), 7.42-7.48 (m, 2 H), 5.00 (s, 1 H), 4.25-4.34 (m, 2 H), 3.70-3.90 (m, 4 H), 1.33-1.37 (t, J = 7.1 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 169.22, 165.13, 132.78, 129.19, 128.88, 126.62, 86.62, 74.59, 62.55, 36.50, 32.39, 14.47. MS (EI): m/z = 467 (0.58) [M⁺(Se⁸⁰,Br⁷⁹,Br⁷⁹)]. Anal. Calcd for C₁₄H₁₅Br₂NO₂Se: C, 35.93; H, 3.23; N, 2.99. Found: C, 36.90; H, 3.41; N, 3.10.