Synthesis of 3-Oxazolines via SnCl4-Promoted Formal [3+2] Cycloaddition of Donor–Acceptor Oxiranes and Nitriles

Hai Zhou; Xiaofei Zeng; Yan Xie; Guofu Zhong

doi:10.1055/s-0034-1380216

Synlett, Table of Contents

Synlett 2015; 26(12): 1693-1696
DOI: 10.1055/s-0034-1380216

letter

Synthesis of 3-Oxazolines via SnCl₄-Promoted Formal [3+2] Cycloaddition of Donor–Acceptor Oxiranes and Nitriles

Authors

Hai Zhou

^aCollege of Chemistry and Materials Engineering, Quzhou University, Quzhou 324000, P. R. of China
Xiaofei Zeng*

^bCollege of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, P. R. of China Email: zgf@hznu.edu.cn Email: 20130078@hznu.edu.cn
Yan Xie

^aCollege of Chemistry and Materials Engineering, Quzhou University, Quzhou 324000, P. R. of China
Guofu Zhong*

^bCollege of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, P. R. of China Email: zgf@hznu.edu.cn Email: 20130078@hznu.edu.cn

Abstract

All articles of this category

Abstract

A novel SnCl₄-promoted formal [3+2] cycloaddition of donor–acceptor oxiranes and nitriles via chemoselective C–C bond breakage was developed. This reaction provides an efficient and practical method for the preparation of 3-oxazolines in good yields (up to 89%).

Key words

synthesis - 3-oxazoline - formal [3+2] cycloaddition - oxirane - nitrile

Full Text

References

References and Notes

1a 1,3-Dipolar Cycloaddition Chemistry . Vol. 1. Padwa A. Wiley; New York: 1984
1b 1,3-Dipolar Cycloaddition Chemistry . Vol. 2. Padwa A. Wiley; New York: 1984
1c Huisgen R In Advances in Cycloaddition . Vol. 1. Curran DP. JAI Press; Greenwich: 1988: 1-32
1d Deshong P, Lander SW, Leginus JM. Jr, Dicken CM In Advances in Cycloaddition . Vol. 1. Curran DP. JAI Press; Greenwich: 1988: 87-128
1e Gothelf KV, Jørgensen KA. Chem. Rev. 1998; 98: 863
1f Kanemasa S. Synlett 2002; 1371
1g The Chemistry of Heterocyclic Compounds: Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products. Vol. 59. Padwa A, Pearson WH. Wiley and Sons; New York: 2002
1h Topics in Heterocyclic Chemistry: Synthesis of Heterocycles via Cycloadditions I. Vol. 12. Hassner A. Springer; Berlin/Heidelberg: 2008

2a Huisgen R. Angew. Chem., Int. Ed. Engl. 1977; 16: 572 ; and references cited therein
2b Bemaus C, Font J, de March P. Tetrahedron 1991; 47: 7713
2c Wang G.-W, Yang H.-T, Wu P, Miao CB, Xu Y. J. Org. Chem. 2006; 71: 4346

3a Hojo M, Ohkuma M, Ishibashi N, Hosomi A. Tetrahedron Lett. 1993; 34: 5943
3b Hojo M, Aihara H, Suginohara Y, Sakata K, Nakamura S.-Y, Murakami C, Hosomi A. J. Org. Chem. 1997; 62: 8610

4a Shimizu N, Bartlett PD. J. Am. Chem. Soc. 1978; 100: 4260
4b Bekhazi M, Warkentin J. J. Am. Chem. Soc. 1983; 105: 1289
4c Bekhazi M, Risbood PA, Warkentin J. J. Am. Chem. Soc. 1983; 105: 5675
4d Couture P, Terlouw JK, Warkentin J. J. Am. Chem. Soc. 1996; 118: 4214
4e Warkentin J. J. Chem. Soc., Perkin Trans. 1 2000; 2161

5a Gill HS, Landgrebe JA. Tetrahedron Lett. 1982; 23: 5099
5b Gill HS, Landgrebe JA. J. Org. Chem. 1983; 48: 1051

6 Hojo M, Aihara H, Hosomi A. J. Am. Chem. Soc. 1996; 118: 3533

7a De March P, Huisgen R. J. Am. Chem. Soc. 1982; 104: 4952
7b Huisgen R, De March P. J. Am. Chem. Soc. 1982; 104: 4953
7c Doyle MP, Forbes DC, Protopopova MN, Stanley SA, Vasbinder MM, Xavier KR. J. Org. Chem. 1997; 62: 7210
7d Jiang B, Zhang X.-B, Luo Z.-H. Org. Lett. 2002; 4: 2453
7e Mehta G, Muthusamy S. Tetrahedron 2002; 58: 9477
7f Lu C.-Y, Chen Z.-Y, Liu H, Hu WH, Mi A.-Q. J. Org. Chem. 2004; 69: 4856
7g Russell AE, Brekan J, Gronenberg L, Doyle MP. J. Org. Chem. 2004; 69: 5269
7h Suga H, Ebiura Y, Fukushima K, Kakehi A, Baba T. J. Org. Chem. 2005; 70: 10782
7i Padwa A. Helv. Chim. Acta 2005; 88: 1357
7j Torssell S, Somfai P. Adv. Synth. Catal. 2006; 348: 2421
7k Son S, Fu GC. J. Am. Chem. Soc. 2007; 129: 1046
7l DeAngelis A, Talor M, Fox JM. J. Am. Chem. Soc. 2009; 131: 1101

8a Zhang J, Chen Z, Wu H.-H, Zhang J. Chem. Commun. 2012; 48: 1817
8b Chen Z, Tian Z, Zhang J, Ma J, Zhang J. Chem. Eur. J. 2012; 18: 8591
8c Chen Z, Wei L, Zhang J. Org. Lett. 2011; 13: 1170
8d Liu R, Zhang M, Zhang J. Chem. Commun. 2011; 47: 12870
8e Zhang J, Xiao Y, Zhang J. Adv. Synth. Catal. 2013; 355: 2793

9a Yu M, Pantos GD, Sessler JL, Pagenkopf BL. Org. Lett. 2004; 6: 1057
9b Sathishkannan G, Srinivasan K. Org. Lett. 2011; 13: 6002
9c Chagarovskiy AO, Budynina EM, Ivanova OA, Trushkov IV. Chem. Heterocycl. Compd. 2010; 46: 120

10 Cui B, Ren J, Wang Z. J. Org. Chem. 2014; 79: 790

11a Chang SS, Hirai C, Reddy BR, Herz KO, Kato A. Chem. Ind. 1968; 1639
11b Peterson RJ, Izzo HI, Jungermann E, Chang SS. J. Food Sci. 1975; 40: 948
11c Ho C.-T, Lee KN, Jin QZ. J. Agric. Food Chem. 1983; 31: 336
11d Tang J, Jin QZ, Shen G.-H, Ho C.-T, Chang SS. J. Agric. Food Chem. 1983; 31: 1287
11e Ho C.-T, Lee M.-H, Chang SS. J. Food Sci. 1981; 47: 127
11f Maga JA. J. Agric. Food Chem. 1978; 26: 1049

12 Dimethyl 4-Phenyl-2-(p-tolyl)oxazole-5,5(2H)-dicarboxylate (3aa) – Typical Procedure To a mixture of dimethyl-3-p-tolyloxiranyl-2,2-dicarboxylate (1a, 0. 25 g, 1 mmol, 1 equiv) and benzonitrile (2a, 0.52g, 5 mmol, 5 equiv) was added SnCl₄ (0.12 mL, 1 mmol, 1 equiv) at 0 °C. The reaction mixture was then stirred at r.t. until the starting materials were consumed as indicated by TLC analysis. The mixture was poured into 50 mL aq sat. NaHCO₃ solution and extracted with CH₂Cl₂ (3 × 25 mL). The combined organic layer was rinsed with H₂O, brine, and dried over anhydrous MgSO₄. The solvent was evaporated off to get a residue which was then purified by flash chromatography to give pure product 3aa (269 mg, 76%). ¹H NMR (500 MHz, CDCl₃): δ = 8.11 (d, J = 7.8 Hz, 2 H), 7.54 (t, J = 7.5 Hz, 1 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.19 (d, J = 7.9 Hz, 2 H), 7.11 (d, J = 7.9 Hz, 2 H), 6.15 (s, 1 H), 3.90 (s, 3 H), 3.20 (s, 3 H), 2.31 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 167.6, 166.0, 162.9, 138.2, 133.5, 132.2, 128.9, 128.9, 128.6, 128.0, 126.6, 90.7, 76.6, 53.8, 52.5, 21.3. HRMS: m/z calcd for C₂₀H₁₉NO₅ [M + H⁺]: 354.1336; found: 354.1330.
13 Crystal Structure Analysis for 7 C₁₈H₁₉NO₃, Mr = 297.35 g mol^–1, monoclinic, space group P121/n1, a = 10.3653 (5), b = 10.0111 (4), c = 14.6662 (6) Å, α = 90.00, β = 93.8990 (10), γ = 90.00, V = 1518.36 (11) Å³, ρ = 1.301 g/cm³, F(000) = 632. X-ray diffraction data were collected on a Nonius Kappa CCD diffractometer at the temperature 296 K using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Structure 7 was solved by direct methods with SIR97 program¹⁴ and refined by full-matrix least squares techniques with anisotropic nonhydrogen atoms. Hydrogen atoms were refined in the riding model. The refinement calculations were carried out with the help of SHELX97 program.¹⁵ ORTEP¹⁶ view of the molecule is shown in the Supporting Information. Crystallographic data for structure 7 have been deposited at the Cambridge Crystallographic Data Centre (CCDC number 1059963. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif).
14 Altomare A, Burla MC, Camalli M, Cascarano GL, Giacovazzo C, Guagliardi A, Moliterni AG. G, Spagna R. J. Appl. Crystallogr. 1999; 115
15 Sheldrick GM. SHELXL97, Program for the Refinement of Crystal Structures . University of Göttingen; Germany: 1997
16 Johnson CK. ORTEP-II, Report ORNL-5138 . Oak Ridge National Laboratory; Oak Ridge (TN, USA): 1976

Supplementary Material

Supporting Information (PDF)