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

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

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

Full Text

References

1a Liu HW. Walsh CT. In The Chemistry of the Cyclopropyl Group Vol. 2: Rappoport Z. Wiley & Sons; New York: 1987. p.959

1b Burger A. Progr. Drug Res. 1971, 15: 227

1c Baldwin JE. Parker DW. J. Org. Chem. 1987, 52: 1475

1d Baldwin JE. Parker DW. Chem. Rev. 2003, issue 4:

2a Gnad F. Reiser O. Chem. Rev. 2003, 103: 1603

2b Wessjohann L. Krass N. Yu D. de Meijere A. Chem. Ber. 1992, 125: 867 ; and references therein

3a Shafiee A. Mazloumi A. Cohen VI. J. Heterocycl. Chem. 1979, 16: 1563

3b Shafiee A. Shafaati A. Khamench BH. J. Heterocycl. Chem. 1989, 26: 709

3c Shafieem A. Khashayarmanesh Z. Kamal F. J. Sci. Islamic Rep. Iran 1990, 1: 111 ; Chem. Abstr. 1991, 115: 49544

4a Huang X. Xie MH. Org. Lett. 2002, 4: 1331

4b Huang X. Xie MH. J. Org. Chem. 2002, 67: 8895

4c Huang X. Sun A. J. Org. Chem. 2000, 65: 6561

Synthesis of MCPs:

5a Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev. 2003, 103: 1213

5b Brandi A. Goti A. Chem. Rev. 1998, 98: 598

5c Yamago S. Nakamura E. Org. React. 2002, 61: 1

5d Nakamura E. Yamago S. Acc. Chem. Res. 2002, 35: 867

5e Yamago S. Takeichi A. Nakamura E. Synthesis 1996, 1380

Reviews:

6a Binger P. Buch HM. Top. Curr. Chem. 1987, 135: 77

6b Ohta T. Takaya H. In Comprehensive Organic Synthesis Vol. 5: Trost BM. Pergamon; Oxford: 1991. p.1185

7a Salaün J. Top. Curr. Chem. 1999, 207: 1

7b Salaün J. Baird MS. Curr. Med. Chem. 1995, 2: 511

7c Huang Z. He YB. Raynor K. Tallent M. Reisine T. Goodman M. J. Am. Chem. Soc. 1992, 114: 9390

7d Zhu YF. Yamazaki T. Tsang JW. Lok S. Goodman M. J. Org. Chem. 1992, 57: 1074

7e Notzel MW. Tamm M. Labahn T. Noltemeyer M. Es-Sayed M. de Meijere A. J. Org. Chem. 2000, 65: 3850

7f Nötzel MW. Labahn T. Es-Sayed M. de Meijere A. Eur. J. Org. Chem. 2001, 3025

8 Sun PP. Chang MY. Chiang MY. Chang NC. Org. Lett. 2003, 5: 1761

For recent examples of selenoamides, see:

9a Pan BC. Chen ZH. Piras G. Dutschman GE. Rowe EC. Cheng YC. Ch SH. J. Heterocycl. Chem. 1994, 177

9b Koketsu M. Senda T. Yoshimura K. Ishihara H. J. Chem. Soc., Perkin Trans. 1 1999, 453

9c Attanasi OA. Filippone P. Perrulli FR. Santeusanio S. Eur. J. Org. Chem. 2002, 2323

9d Koketsu M. Takenaka Y. Hiramatsu S. Ishihara H. Heterocycles 2001, 55: 1181

9e Koketsu M. Hiramatsu S. Ishihara H. Chem. Lett. 1999, 485

9f Zhang PF. Chen ZC. Synthesis 2000, 1219

9g Koketsu M. Kanoh M. Itoh E. Ishihara H. J. Org. Chem. 2001, 66: 4099

9h Koketsu M. Takenaka Y. Ishihara H. Synthesis 2001, 38: 503

9i Zhang PF. Chen ZC. J. Heterocycl. Chem. 2001, 38: 503

9j Ishihara H. Koketsu M. Fukuta Y. Nada F. J. Am. Chem. Soc. 2001, 123: 8408

9k Bhattacharyya P. Woollins JD. Tetrahedron Lett. 2001, 42: 5949

9l Koketsu M. Okayama Y. Aoki H. Ishihara H. Heteroat. Chem. 2002, 13: 195

9m Zhao H.-R. Zhao X.-J. Huang X. Synth. Commun. 2002, 32: 3383

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.

11a Huang X. Zhou HW. Org. Lett. 2002, 4: 4419

11b Zhou HW. Huang X. Chen WL. Synlett 2003, 2080

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.

13a Lai LL. Reid DH. Synthesis 1993, 870

13b Zhao HR. Ruan MD. Fan WQ. Zhou XJ. Synth. Commun. 1994, 24: 1761