Silver Acetate Catalysed Asymmetric 1,3-Dipolar Cycloadditions of Imines and Chiral Acrylamides

Miklós Nyerges; David Bendell; Andrea Arany; David E. Hibbs; Simon J. Coles; Michael B. Hursthouse; Paul W. Groundwater; Otto Meth-Cohn

doi:10.1055/s-2003-39325

LETTER

Silver Acetate Catalysed Asymmetric 1,3-Dipolar Cycloadditions of Imines and Chiral Acrylamides

Miklós Nyerges*^a, David Bendell^b, Andrea Arany^b, David E. Hibbs^c, Simon J. Coles^d, Michael B. Hursthouse^d, Paul W. Groundwater^b, Otto Meth-Cohn^b
^a Research Group of the Hungarian Academy of Sciences, Department of Organic Chemical Technology, Technical University of Budapest, 1521 Budapest P.O.B. 91, Hungary
e-Mail: mnyerges@mail.bme.hu;
^b Institute of Pharmacy and Chemistry, School of Sciences, University of Sunderland, Sunderland, SR1 3SD, UK
^c Department of Chemistry, Cardiff University, P.O. Box 912, Cardiff, CF1 3TB, UK
^d Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

Abstract

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Abstract

N-Metallated azomethine ylides 5 were generated by the reaction of arylidene glycine imines 1 with AgOAc and triethylamine. These azomethine ylides undergo cycloaddition to chiral acrylamides 2 with excellent diastereoselectivity. The configuration of two of the cycloadducts (3a ₁ and 3c ₁) has been confirmed by X-ray crystallography.

Key words

cycloaddition - azomethine ylides - pyrrolidine - asymmetric

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References

1a 1,3-Dipolar Cycloaddition Chemistry Vol. 1: Padwa A. Wiley; New York: 1984.

1b 1,3-Dipolar Cyclo-addition Chemistry Vol. 2: Padwa A. Wiley; New York: 1984.

1c Synthetic Applications of 1,3-Dipolar Cycloaddition-Chemistry toward Heterocycles and Natural Products Padwa A. Pearson WH. Wiley; New York: 2002.

2a Garner P. Ho WB. Grandhee SK. Youngs WJ. Kennedy VO. J. Org. Chem. 1991, 56: 5893

2b Garner P. Ho WB. Shin C. J. Am. Chem. Soc. 1993, 115: 10742

2c Monn JA. Valli MJ. J. Org. Chem. 1994, 59: 2773

2d Pham VC. Charlton JL. J. Org. Chem. 1995, 60: 8051

2e Fishwick CWG. Foster RJ. Carr RE. Tetrahedron Lett. 1996, 37: 3915

2f Daubié C. Mutti S. Tetrahedron Lett. 1996, 37: 7743

3 Gothelf KV. Jørgensen KA. Chem. Rev. 1998, 98: 863

4a Regan AC. J. Chem. Soc., Perkin Trans. 1 1999, 357

4b Park DH. Kim SD. Kim SM. Kim JD. Kim YH. Chem. Commun. 1999, 963

4c Kitagawa O. Izawa H. Taguchi T. Tetrahedron Lett. 1997, 38: 4447

4d Waldmann H. Liebigs Ann. Chem. 1990, 671

5a Barr DA. Dorrity MJ. Grigg R. Hargreaves S. Malone JF. Montgomery J. Redpath J. Stevenson P. Thornton-Pett M. Tetrahedron 1995, 51: 273

5b Keller E. De Lange B. Rispens MT. Feringa BL. Tetrahedron 1993, 49: 8899

6a Karlsson S. Högberg H.-E. Tetrahedron: Asymmetry 2001, 12: 1977

6b Ling R. Ekhato IV. Rubin R. Wustrow DJ. Tetrahedron 2001, 57: 6579

7a Kanemasa S. Hayashi T. Tanaka J. Yamamoto H. Sakurai T. J. Org. Chem. 1991, 56: 4473

7b Annunziata R. Cinquini M. Cozzi F. Raimondi L. Pilati T. Tetrahedron: Asymmetrie 1991, 2: 1329

8 Galley G. Liebscher J. Pätzel M. J. Org. Chem. 1995, 60: 5005

9a Fray AH. Meyers AI. J. Org. Chem. 1996, 61: 3362

9b Kopach ME. Fray AH. Meyers AI. J. Am. Chem. Soc. 1996, 118: 9876

10a Waldmann H. Blaeser E. Jansen M. Letschert HP. Chem.-Eur. J. 1995, 1: 150

10b Waldmann H. Blaeser E. Jansen M. Letschert HP. Angew. Chem., Int. Ed. Engl. 1994, 33: 1329

11 O’Brien P. J. Chem. Soc., Perkin Trans. 1 1998, 1439

All amines were purchased from Sigma-Aldrich Chemical Co. except for the precursor of 2d which was prepared by a known literature procedure:

12a Chong MJ. Clark IS. Koch I. Olbach P. Taylor NJ. Tetrahedron: Asymmetry 1995, 6: 409

12b Useful note on the original method: Taber DF. Gorski GJ. Liable-Sands LM. Rheingold AL. Tetrahedron. Lett. 1997, 38: 6317

13a Cardillo G. Hashem A. Tomasini C. J. Chem. Soc., Perkin Trans. 1 1990, 1487

13b Benovsky P. Stephenson GA. Stille JR. J. Am. Chem. Soc. 1998, 2493

14 Gutiérrez-García VM. López-Ruiz H. Reyes-Rangel G. Juaristi E. Tetrahedron 2001, 57: 6487

15 Blaschke G. Chem. Ber. 1974, 107: 237

16a Nyerges M. Rudas M. Tóth G. Herényi B. Bitter I. Tõke L. Tetrahedron 1995, 51: 13321

16b Pak CS. Nyerges M. Synlett 1999, 1271

16c Nyerges M. Fejes I. Tõke L. Synthesis 2002, 1823

17

Silver Acetate Catalysed Cycloaddition Reactions - General procedure: A mixture of imine (1.2 equiv) AgOAc (1.5 equiv), appropriate dipolarophile (1 equiv) and Et₃N in dry toluene (5 mL for 1 mmol of imine) protected from the light with aluminium foil was stirred at r.t. for 12-48 h. The reaction was then quenched by addition of sat. aq NH₄Cl solution and Et₂O. The mixture was filtered through a pad of Celite^®. The organic layer was separated, washed with H₂O, brine and dried over MgSO₄, filtered and the solvent evaporated. The residue was purified by flash chromatography and/or recrystallisation to afford the cycloadducts. Selected data for representative examples: ( S , S , S , R )-Ethyl-5-(2,4-dichlorophenyl)-4-[(1′-phenyl-ethyl)carbamoyl]-pyrrolidine-2-carboxylate ( 4b ₂ ). White powder; mp 171-172 °C. [α]_d ²³ = +116 (c 1.2, CHCl₃). ¹H NMR (270 MHz, CDCl₃): δ = 7.51 (d, 1 H, J = 7.9 Hz, Ar), 7.33-7.12 (m, 5 H, Ar), 6.93 (dd, 1 H, J = 1.8 Hz and 7.9 Hz, Ar), 6.42 (d, 1 H, J = 1.8 Hz, Ar), 4.73 (m, 1 H, CHCH₃), 4.57 (d, 1 H, J = 6.0 Hz, H-5), 4.29 (q, 2 H, OCH₂), 3.96 (dd, 1 H, J = 6.1 Hz and 9.5 Hz, H-2), 3.35 (ddd, 1 H, J = 3.2 Hz, 6.0 Hz and 6.7 Hz, H-4), 2.70 (br s, 1 H, NH), 2.53 (ddd, 1 H, J = 6.7 Hz, 9.5 Hz and 13.8 Hz, H₂-3), 2.35 (ddd, 1 H, J = 3.2 Hz, 6.1 Hz and 13.8 Hz, H₂-3), 1.29 (t, 3 H, J = 7.3 Hz, Me), 1.08 (d, 3 H, J = 8.6 Hz, Me). ¹³C NMR: δ = 173.4 (C=O), 170.9 (C=O), 143.0 (q), 134.5 (q), 133.8 (q), 133.3 (q), 129.1 (2 × CH), 128.6 (2 × CH), 127.6 (CH), 127.6 (CH), 126.4 (CH), 125.9 (CH), 62.6, 61.2, 58.1, 47.3, 33.6, 21.0, 14.2, IR (nujol): 3306, 1734, 1644, 1527, 1213, 1123, 1090, 1050, 1019 cm^-1. MS (CI): m/z (rel. intensity, %) = 477 (4)[M⁺], 463 (12), 435 (base peak), 401 (15), 361 (14), 262 (17), 140 (20), 105 (34). HRMS: Calcd 434.1164 for C₂₂H₂₄Cl₂N₂O₃. Found: 434.1152. ( R , R , R , R , R )-Ethyl-5-phenyl-4-{[bis(1′-phenyl-ethyl)]carbamoyl}-pyrrolidine-2-carboxylate ( 3c ₁ ). Colourless needles; mp 172-173 °C. [α]_d ²³ = -158 (c 0.96, CHCl₃). ¹H NMR (270 MHz, CDCl₃): δ = 7.31-7.02 (m, 11 H, Ph), 6.77-6.71 (m, 4 H, Ph), 5.31 (broad d, 1 H, J = 6.6 Hz, PhCH), 4.70 (q, 1 H, J = 7.3 Hz, PhCH), 4.23 (dq, 2 H, J = 1.9 and 7.3 Hz, OCH₂), 3.95 (d, 1 H, J = 7.3 Hz, H-5), 3.87 (t, 1 H, J = 8.6 Hz, H-2), 3.43 (dd, 1 H, J = 5.3 Hz and 7.3 Hz, H-4), 2.53-2.02 (m, 2 H, H₂-3), 1.46 (d, 3 H, J = 7.3 Hz, CH₃), 1.42 (d, 3 H, J = 7.3 Hz, CH₃), 1.29 (t, 3 H, J = 7.3 Hz, CH₃). ¹³C NMR: δ = 173.9 (C=O), 173.1 (C=O), 141.1 (2 × Ph-1′C), 138.7 (Ph-1′C), 128.4, 128.3, 128.0, 127.8, 127.2, 126.9 (15 × CH, overlapping), 67.4, 61.0, 52.4, 52.1, 47.2, 36.9, 30.0, 19.5, 16.9, 14.3. IR (nujol): 1737, 1627, 1604, 1453, 1293, 1262, 1195, 1177, 1102, 1025, 949 cm^-1. MS (CI): m/z (rel. intensity, %) = 471 (base peak) [M⁺], 397 (10), 367 (15), 280 (12), 246 (9), 105 (22). HRMS: Calcd 470.2569 for C₃₀H₃₄N₂O₃. Found: 470.2573. ( R , R , R , R , R )-Ethyl-5-(4-nitrophenyl)-4-[(2′,5′- trans -diphenylpyrrolidinyl)-1-carbonyl]-pyrrolidine-2-carboxylate ( 3d ₃ ). White powder; mp 222-223 °C. [α]_d ²³ = +34 (c 0.17, CHCl₃). ¹H NMR (270 MHz, CDCl₃):
δ = 8.09 (d, 2 H, J = 8.6 Hz, Ar), 7.44-7.31 (m, 5 H, Ar), 7.18 (d, 2 H, J = 6.6 Hz, Ar), 7.07 (t, 1 H, J = 7.3 Hz, Ar), 6.95 (t, 2 H, J = 7.3 Hz, Ar), 6.52 (d, 2 H, J = 7.3 Hz, Ar), 5.25 (d, 1 H, J = 7.3 Hz, CHPh), 5.16 (d, 1 H, J = 7.3 Hz, CHPh), 4.24 (d, 1 H, J = 7.3 Hz, H-5), 4.20 (q, 2 H, J = 7.3 Hz, OCH₂), 3.69 (t, 1 H, J = 8.6 Hz, H-2), 3.25 (ddd, 1 H, J = 3.3 Hz, 4.6 Hz and 7.9 Hz, H-4), 2.51-2.19 (m, 2 H, CH₂), 2.01 (ddd, 1 H, J = 4.6 Hz, 7.3 Hz and 13.2 Hz, H₂-3), 1.88-1.72 (m, 2 H, CH₂), 1.58 (dd, 1 H, J = 5.3 Hz and 11.9 Hz, CH₂), 1.27 (t, 3 H, J = 7.3 CH₃). ¹³C NMR: δ = 172.9 (C=O), 172.2 (C=O), 147.1 (q), 146.2 (q), 143.6 (q), 142.6 (q), 129.0 (2 × CH), 127.9 (2 × CH), 127.8 (2 × CH), 127.7 (2 × CH), 126.6 (CH), 125.4 (2 × CH), 125.1 (2 × CH), 123.6 (2 × CH), 66.1, 63.2, 62.0, 61.1, 60.2, 47.8, 36.3, 33.4, 30.0, 14.2. IR (nujol): 1736, 1611, 1511, 1416, 1353, 1309, 1272, 1187, 1171, 1063, 1028 cm^-1. MS (CI): m/z (rel. intensity, %) = 514 (base peak) [M⁺¹], 484 (12), 440 (8), 278 (10), 237 (12). HRMS: Calcd 513.2264 for C₃₀H₃₁N₃O₅. Found: 513.2239. ( R , R , R , R , S )-Ethyl-4-[(2′-hydroxy-1′-methyl-2′-phenyl-ethyl)carbamoyl]-5-(2,4-dichlorophenyl)-pyrrolidine-2-carboxylate ( 3e ₁ ). White powder; mp 182-183 °C. [α]_d ²³ = -101 (c 1.0, CHCl₃). ¹H NMR (270 MHz, CDCl₃):
δ = 7.40-7.15 (m, 8 H, Ar), 4.61 (d, 1 H, J = 6.6 Hz, CHOH), 4.40 (d, 1 H, J = 4.0 Hz, H-5), 4.27 (dq, 2 H, J = 1.9 and 7.3 Hz, OCH₂), 4.10 (broad m, 2 H, OH + CH-CH₃), 3.84 (t, 1 H, J = 7.9 Hz, H-2), 3.57 (ddd, 1 H, J = 4.0 Hz, 7.3 Hz and 10.7 Hz, H-4), 2.80 (m, 1 H, H₂-3), 2.47 (s, 3 H, NMe), 2.35 (m, 1 H, H₂-3), 1.33 (t, 3 H, J = 7.3 Hz, CH₃), 0.72 (d, 3 H, J = 7.3 Hz, CH₃). ¹³C NMR: δ = 173.6 (C=O), 172.8 (C=O), 141.7, 134.7, 133.7, 133.2, 129.2, 128.5, 127.9 (2 × CH), 127.3, 127.1, 126.1 (2 × CH), 76.5, 62.3, 59.8, 56.8, 43.5, 34.8, 32.5, 14.2, 11.4. IR (KBr): 3377, 2987, 1736, 1621, 1476, 1449, 1413, 1374, 1206, 1104, 1048 cm^-1. MS (CI):
m/z (rel. intensity, %) = 479 (base peak) [M⁺], 463 (20), 314 (31), 280 (15), 176 (10), 148 (52), 135 (22), 107 (25). HRMS: Calcd 478.1426 for C₂₄H₂₈Cl₂N₂O₄. Found: 478.1409.

18a Groundwater PW. Sharif T. Arany A. Hibbs DE. Hurthouse MB. Nyerges M. Tetrahedron Lett. 1998, 38: 1433

18b Groundwater PW. Sharif T. Arany A. Hibbs DE. Hurthouse MB. Garnett I. Nyerges M. J. Chem. Soc., Perkin Trans. 1 1998, 2837