Synlett 2017; 28(11): 1341-1345
DOI: 10.1055/s-0036-1588751
letter
© Georg Thieme Verlag Stuttgart · New York

A Novel Route to 2-Arylquinolines: Reductive Cleavage of 2′-Nitroaryl-∆2-isoxazolines

Prashantha Kamath
a  Syngenta Biosciences Pvt. Ltd., Santa Monica Works, Corlim, Ilhas, Goa-403110, India
,
Russell C. Viner
b  Syngenta Jealott’s Hill International Research Centre, Bracknell, Berkshire, RG42 6EY, UK   Email: [email protected]
,
Stephen C. Smith
b  Syngenta Jealott’s Hill International Research Centre, Bracknell, Berkshire, RG42 6EY, UK   Email: [email protected]
,
Mukul Lal*
a  Syngenta Biosciences Pvt. Ltd., Santa Monica Works, Corlim, Ilhas, Goa-403110, India
› Author Affiliations
Further Information

Publication History

Received: 10 January 2017

Accepted after revision: 22 February 2017

Publication Date:
20 March 2017 (online)


The article is dedicated to Prof. Dr. Michael Schmittel on the occasion of his 60th birthday.

Abstract

A novel synthetic route for the synthesis of quinolines starting from Δ2-isoxazolines under reductive conditions is reported. The ­reductive cyclization to quinolines is achieved under both metal and metal-free conditions. The reaction proceeds via an intramolecular N–H···O hydrogen bond intermediate, accelerating the reductive cleavage 1000-fold (DFT calculations) in comparison with non-hydrogen bonded system.

Supporting Information

 
  • References and Notes

  • 1 Pasteris RJ, Hanagan MA, Bisaha JJ, Finkelstein BL, Hoffman LE, Gregory V, Shepherd CP, Andreassi JL, Sweigard JA, Klyashchitsky BA, Henry YT, Berger A. ACS Symp. Ser. 2015; 1204: 149-149
  • 2 Zhang Y.-b. Shijie Nongyao 2015; 37: 4-4
  • 3 Kaur K, Kumar V, Sharma AK, Gupta GK. Eur. J. Med. Chem. 2014; 77: 121-121
  • 4 Imran M, Khan SA, Siddiqui N. Indian J. Pharm. Sci. 2004; 66: 377-377
  • 5 Kumar GR, Kotian SY, Kudva NN. U, Banerjee K, Vicas CS, Rai KM. L, Rai VR, Byrappa K. J. Chem. Biol. Phys. Sci. 2016; 6: 128-128
  • 6 Lam K.-H, Ho SS.-W, Lam P.-L, Tang JC.-O, Bian Z.-X, Chan AS.-C, Li H, Wong W.-Y, Chui C.-H. Chin. Chem. Lett. 2014; 25: 1165-1165
  • 7 Shirini F, Beigbaghlou SS, Atghia SV, Mousazadeh SA.-R. Dyes Pigm. 2013; 97: 19-19
  • 8 Illy H, Funderburk L. Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons; New York: 1968. 2nd ed., Vol. 16 886
  • 9 Song Y, Wang H, Zhang L, Qi Y, Li Y, Zeng W, Zeng Q, Gu X, Liu T, Wang Z, Zhu J. CN105175333A, 2015
  • 10 Dzhemilev UM, Ibragimov AG, Galimzyanova NF, Rakhimova EB, Vasileva IV. RU2565783C1, 2015
  • 11 Luo K. CN104672215A, 2015
  • 12 Tang J, Fan H, Li Y. CN104650075A, 2015
  • 13 Kumar KA, Govindaraju M, Renuka N, Kumar GV. J. Chem. Pharm. Res. 2015; 7: 250-250
  • 14 Sankar U, Surya Kumar CV, Subramanian V, Balasubramanian KK, Mahalakshimi S. J. Org. Chem. 2016; 81: 2340-2340
  • 15 Nagireddy JR, Raheem M.-A, Haner J, Tam W. Curr. Org. Synth. 2011; 8: 659-659
  • 16 Kozikowski AP. Acc. Chem. Res. 1984; 17: 410-410
  • 17 Coffman KC, Palazzo TA, Hartley TP, Fettinger JC, Tantillo DJ, Kurth MJ. Org. Lett. 2013; 15: 2062-2062
  • 18 Palazzo TA, Patra D, Yang JS, El Khoury E, Appleton MG, Haddadin MJ, Tantillo DJ, Kurth MJ. Org. Lett. 2015; 17: 5732-5732
  • 19 Jiang D, Chen Y. J. Org. Chem. 2008; 73: 9181-9181
  • 20 Minakata S, Okumura S, Nagamachi T, Takeda Y. Org. Lett. 2011; 13: 2966-2966
  • 21 Mendelsohn BA, Lee S, Kim S, Teyssier F, Aulakh VS, Ciufolini MA. Org. Lett. 2009; 11: 1539-1539
  • 22 Shailaja AM. M, Rao BV. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2011; 50: 214-214
  • 23 Mohammed S, Vishwakarma RA, Bharate SB. RSC Adv. 2015; 5: 3470-3470
  • 24 Kadam HK, Tilve SG. RSC Advances 2015; 5: 83391-83391
  • 25 2-Nitroaryl-Δ2-isoxazoline Derivatives 1am: General Procedure To a solution of the oxime (1.00 mmol, 1.0 equiv) in DMF (2.0 mL) at r.t. was added N-chlorosuccinimide (1.10 mmol, 1.10 equiv) and the mixture was stirred for 60 min. To the reaction mixture was added the alkene in one portion (1.10 mmol, 1.1 equiv) followed by a solution of triethylamine (1.00 mmol, 1.00 equiv) in DMF (1.0 mL). After complete addition, the reaction mixture was stirred at 23–25 °C until complete conversion of the in situ formed chlorooxime intermediate (reaction was monitored by TLC). After complete conversion, the reaction was poured into cold water (30.0 mL) and stirred for 10 min. The aqueous phase was extracted with ethyl acetate (3 × 20.0 mL), the combined organic layers were washed with brine (20.0 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield the crude product which was purified by flash chromatography. 3,5-Bis(2-nitrophenyl)-4,5-dihydroisoxazole (1g) White solid; yield: 241 mg (77%); mp 120–121 °C. 1H NMR (CDCl3, 400 MHz): δ = 8.18 (dd, J = 8.3, 1.3 Hz, 2 H), 8.07 (dd, J = 8.0, 1.3 Hz, 2 H), 7.91 (dd, J = 7.9, 1.4 Hz, 2 H), 7.69–7.80 (m, 4 H), 7.52–7.65 (m, 6 H), 6.42 (d, J = 6.3 Hz, 1 H), 6.39 (d, J = 6.3 Hz, 1 H), 4.04 (d, J = 6.0 Hz, 1 H), 3.27 (d, J = 6.3 Hz, 1 H), 3.22 (d, J = 6.3 Hz, 1 H). 13C NMR (CDCl3, 101 MHz): δ = 154.1, 145.4, 142.2, 136.3, 133.5, 132.6, 130.0, 129.9, 128.0, 127.0, 124.1, 124.0, 123.9, 78.7, 45.2. HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H11N3O5: 313.0698; found: 313.0698. tert-Butyl 2-methyl-4-[5-(2-nitrophenyl)-4,5-dihydroisoxazol-3-yl]benzoate (1h) White solid; yield: 313 mg (82%); mp 167–168 °C. 1H NMR (CDCl3, 400 MHz): δ = 8.18 (dd, J = 8.3, 1.3 Hz, 1 H), 7.83–7.87 (m, 2 H), 7.71 (t, J = 7.6 Hz, 1 H), 7.49–7.54 (m, 3 H), 4.15 (dd, J = 17.3, 11.3 Hz, 1 H), 3.26 (dd, J = 17.3, 6.8 Hz, 1 H), 2.58 (s, 3 H), 1.57–1.62 (s, 9 H). 13C NMR (CDCl3, 101 MHz): δ = 166.5, 155.7, 139.8, 137.7, 134.5, 133.4, 131.4, 130.7, 129.7, 128.8, 127.6, 125.2, 123.9, 81.6, 79.3, 43.9, 28.2, 21.7. HRMS (ESI-TOF): m/z [M + H]+ calcd for C21H22N2O5: 382.1528; found: 382.1525. 2-Arylquinoline Derivatives 3; General Procedure 1 To a solution of Δ2-isoxazoline derivative 1 (1.00 mmol, 1.0 equiv) in ethanol (7.0 mL) at 25 °C were added iron powder (8.00 mmol, 8.0 equiv), ammonium chloride (8.00 mmol, 8.0 equiv) and water (7.0 mL). The resulting suspension was stirred at 80 °C for 6 hours and monitored by TLC and LC-MS. The reaction mixture was allowed to cool to 25 °C, and filtered through a bed of Celite®. The filtrate was distilled under reduced pressure and the resulting aqueous phase was extracted with ethyl acetate (3 × 5.0 mL). The combined organic layers were washed with water (5.0 mL) followed by brine (5.0 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield the crude product which was purified by column chromatography to yield pure 3. 2-(4-Chloro-2-fluorophenyl)quinoline (3c) White solid; yield: 206 mg (80%); mp 85–86 °C. 1H NMR (CDCl3, 400 MHz): δ = 8.26 (s, 2 H), 8.20–8.25 (m, 7 H), 8.15 (s, 1 H), 8.13 (s, 2 H), 8.11 (s, 1 H), 7.86–7.90 (m, 9 H), 7.77 (ddd, J = 8.5, 7.0, 1.4 Hz, 5 H), 7.59 (ddd, J = 8.1, 7.0, 1.3 Hz, 5 H), 7.32–7.35 (m, 5 H), 7.27 (s, 6 H), 7.24 (d, J = 2.0 Hz, 2 H), 1.72 (br s, 7 H). 13C NMR (CDCl3, 101 MHz): δ = 161.8–159.3 (d, J = 254 Hz, 1 C), 132.5, 130.0, 129.5, 128.5, 127.5, 127.3, 127.0, 125.2, 124.3, 122.2, 122.1, 121.5, 117.2, 116.9. HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H9ClFN: 257.0407; found: 257.0401. 4-Chloro-3 -(2-quinolyl)aniline (3i) Off-white gum; yield: 188 mg (74%). 1H NMR (CDCl3, 400 MHz): δ = 8.18–8.23 (m, J = 8.5 Hz, 2 H), 7.86 (dd, J = 8.0, 1.3 Hz, 1 H), 7.69–7.78 (m, 2 H), 7.57 (ddd, J = 8.2, 7.0, 1.1 Hz, 1 H), 7.20–7.28 (m, 1 H), 7.02 (d, J = 3.0 Hz, 1 H), 6.68 (dd, J = 8.5, 2.8 Hz, 1 H). 13C NMR (CDCl3, 101 MHz): δ = 157.5, 147.6, 145.6, 139.6, 136.0, 130.8, 129.9, 129.3, 127.6, 127.2, 126.9, 123.0, 121.2, 118.0, 116.9. HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H11ClN2: 254.0610; found: 254.0611.
  • 26 Reichardt C, Welton T. Solvents and Solvent Effects in Organic Chemistry. 4th. ed. Wiley-VCH; Weinheim: 2010
  • 27 Vellanki BP, Batchelor B, Abdel-Wahab A. Environ. Eng. Sci. 2013; 30: 264-264
  • 28 Kumar BP. V, Prathibha A, Shruthi N. Synth. Commun. 2014; 44: 3414-3414
  • 29 Yang LL. D, Fokas D, Yu L, Baldino CM. Synthesis 2005; 47-47
  • 30 Oda S, Shimizu H, Aoyama Y, Ueki T, Shimizu S, Osato H, Takeuchi Y. Org. Process Res. Dev. 2012; 16: 96-96
  • 31 Park BS. K. S. M. J. Electrochem. Soc. 1995; 142: 26-26
  • 32 2-Arylquinoline Derivatives 3; General Procedure 2 To a solution of 2′-nitroaryl-Δ2-isoxazoline 1 (1.00 mmol, 1.0 equiv) in DMSO (7.0 mL) was added sodium dithionite (6.00 mmol, 6.0 equiv) at r.t. The suspension was warmed to 100 °C and stirred for 3–5 h. The reaction was monitored by TLC and LC-MS and, after complete conversion, the reaction mixture was cooled to 25 °C. The reaction mixture was poured into an icecold solution of sodium hydroxide and stirred for 10 min. The aqueous phase was extracted with diethyl ether (3 × 10.0 mL) and the combined organic layers were washed with water (10.0 mL) followed by brine (10.0 mL), dried over anhydrous sodium sulfate, filtered and the filtrate was concentrated under reduced pressure to give the crude product which was purified by flash chromatography. 2-(2,4,6-Trifluorophenyl)quinoline (3l) White solid; yield: 137 mg (53%); mp 97–98 °C. 1H NMR (CDCl3, 400 MHz): δ = 8.26 (d, J = 8.2 Hz, 1 H), 8.19 (d, J = 8.2 Hz, 1 H), 7.88 (d, J = 8.3 Hz, 1 H), 7.77 (ddd, J = 8.5, 7.0, 1.4 Hz, 1 H), 7.60 (t, J = 7.5 Hz, 1 H), 7.54 (d, J = 8.5 Hz, 1 H), 6.83 (t, J = 8.0 Hz, 2 H). 13C NMR (CDCl3, 101 MHz): δ = 164.1–159.5 (m, 3 C), 149.1, 148.2, 136.5, 130.0, 129.7, 127.6, 127.3, 127.1, 123.2, 101.0–100.4 (m, 2 C). HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H8F3N: 259.0608; found: 259.0608.