Organic Reactions in Water: An Efficient Synthesis of Pyranocoumarin Derivatives

Abstract

A mild and efficient protocol for the synthesis of pyrano[3,2-c]coumarins from 4-hydroxycoumarin through a one-pot ­reaction in water under phase-transfer conditions has been developed.

Key words

pyranocoumarin - isocyanide - PTC - water - green chemistry

References and Notes

• 1a McKee TC. Covington CD. Fuller RW. Bokesch HR. Young S. Cardellina JH. Kadushin MR. Soejarto DD. Stevens PF. Cragg GM. Boyd MR.
  J. Nat. Prod.  1998,  61:  252 
• 1b Melliou E. Magiatis P. Mitaku S. Skaltsounis A.-L. Chinou E. Chinou I. J. Nat. Prod.  2005,  68:  8 
• 1c Kostova I. Curr. Med. Chem.  2005,  5:  29 
• 1d Basile A. Sorbo S. Spadaro V. Bruno M. Maggio A. Faraone N. Rosselli S. Molecules  2009,  14:  939 
• 2 Ju Y. Still CC. Sacalis JN. Li J. Ho CT. Phytother. Res.  2001,  15:  441 
• 3 Kapoor SK. Kohli JM. Sharma YN. Zaman A. Phytochemistry  1972,  11:  477 
• 4 Duh C.-Y. Wang S.-K. Wu Y.-C. Phytochemistry  1991,  30:  2812 
• 5a Mali RS. Joshi PP. Sandhu PK. Manekar-Tilve A. J. Chem. Soc., Perkin Trans. 1  2002,  371 ; and references cited therein
• 5b Xie L. Takeuchi Y. Cosentino LM. McPhail AT. Lee KH. J. Med. Chem.  2001,  44:  664 
• 5c Nicolaides DN. Gautam DR. Litinas KE. Hadjipavlou-Litina DJ. Fylaktakidou KC. Eur. J. Med. Chem.  2004,  39:  323 
• 5d Melliou E. Magiatis P. Mitaku S. Skaltsounis A.-L. Chinou E. Chinou I. J. Nat. Prod.  2005,  68:  78 
• 5e Galinis DL. Fuller RW. McKee TC. Cardellina JH. Gulakowski RJ. McMahon JB. Boyd MR. J. Med. Chem.  1996,  39:  507 
• 6 Mali RS. Pandhare NA. Sindkhedkar MD. Tetrahedron Lett.  1995,  36:  7109 
• For some selected examples, see:
• 7a Moreau J. Hubert C. Batany J. Toupet L. Roisnel T. Hurvois J.-P. Renaud J.-L. J. Org. Chem.  2009,  74:  8963 
• 7b Appendino G. Cravotto G. Giovenzana GB. Palmisano G. J. Nat. Prod.  1999,  62:  627 
• 7c Nair V. Vinod AU. Ramesh R. Menon RS. Varma L. Mathews S. Chiaroni A. Heterocycles  2002,  58:  147 
• 7d Page PCB. Appleby LF. Day D. Chan Y. Buckley BR. Allin SM. McKenzie MJ. Org. Lett.  2009,  11:  1991 
• 7e Shen Y.-C. Wang L.-T. Chen C.-Y. Tetrahedron Lett.  2004,  45:  187 
• 7f Litinas KE. Symeonidis TS. Tetrahedron  2010,  66:  1289 
• 8a Yadav JS. Subba Reddy BV. Shubashree S. Sadashiv K. Krishna Rao D. J. Mol. Catal. A: Chem.  2007,  272:  128 
• 8b Heravi MM. Baghernejad B. Oskooie HA. Hekmatshoar R. Tetrahedron Lett.  2008,  49:  6101 
• 8c Alizadeh A. Rostomnia S. Esmaili AA. Synthesis  2007,  709 
• 8d Vasuki G. Kumaravel K. Tetrahedron Lett.  2008,  49:  5636 
• 9a De Silva RA. Santra S. Andreana PR. Org. Lett.  2008,  10:  4541 
• 9b Shaabani A. Ali Rezayan H. Ghasemi S. Sarvary A. Tetrahedron Lett.  2009,  50:  1456 
• 9c Heravi MM. Baghernejad B. Oskooie HA. Tetrahedron Lett.  2009,  50:  767 
• 9d Fujiwara S. Asanuma Y. Shin-ike T. Kambe N. J. Org. Chem.  2007,  72:  8087 
• For selected reviews, see:
• 10a Koldobskii GI. Ostrovskii VA. Chem. Heterocycl. Compd.  1983,  19:  1141 
• 10b Shen Z.-X. Kong A.-D. Chen W.-X. Zhang Y.-W. Chin. J. Org. Chem.  2003,  23:  10 
• 10c Ooi T. Maruoka K. Angew. Chem. Int. Ed.  2007,  46:  4222 
• 11a Sarma R. Prajapati D. Synlett  2008,  3001 
• 11b Prajapati D. Gohain M. Thakur AJ. Bioorg. Med. Chem. Lett.  2006,  16:  3537 
• 11c Prajapati D. Thakur AJ. Tetrahedron Lett.  2005,  46:  1433 
• 11d Gohain M. Prajapati D. Gogoi BJ. Sandhu JS. Synlett  2004,  1179 
• 13a

  Typical procedure for the synthesis of 4a-l:
  A mixture of alkyl isocyanide (1 mmol), dialkyl acetylene-dicarboxylate (1 mmol) and 1,3-dicarbonyl compound (1 mmol) in H₂O (5 mL), in the presence of TBAB (10 mol%) was stirred at 80 ˚C until the reaction was complete as indicated by TLC. The crude solid product was filtered, washed with H₂O, dried and purified by column chromatography (EtOAc-hexane, 3:7). The products thus obtained were characterized by their IR, NMR spectroscopic and mass spectrometric data. Dimethyl 2-(cyclohexyl-amino)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3,4-dicarboxylate (4a): White solid; mp 198-200 ˚C; IR (CHCl₃): 3264.9 (N-H), 1732.6, 1686.3, 1659.4 (C=O) cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 1.37-2.09 (m, 10 H, 5 × CH₂), 3.71 (s, 3 H, OCH₃), 3.74 (s, 3 H, OCH₃), 3.78-3.87 (m, 1 H, NCH), 4.73 (s, 1 H, CH), 7.30-7.72 (m, 4 H, ArH), 8.70 (s, 1 H, NH); ^¹³C NMR (75 MHz, CDCl₃): δ = 24.41, 24.46, 25.3, 33.4, 33.7, 36.3, 50.6, 51.2, 52.7, 72.1, 102.9, 113.5, 117.1, 121.9, 124.6, 132.7, 152.7, 154.9, 158.2, 160.7, 169.3, 173.1. GC/MS: m/z = 413 [M⁺]

• 13b

  Typical procedure for the synthesis of 9: An equimolar mixture of ylidine malononitrile 8 (1 mmol) and 4-hydroxycoumarin (1 mmol) in H₂O (5 mL), in the presence of TBAB (10 mol%) was stirred at 80 ˚C until the reaction was complete as indicated by TLC. The solid product was filtered, washed with water, dried and purified by recrystallization (EtOH-CHCl₃, 1:1). The products thus obtained were characterized by their IR, NMR spectroscopic and mass spectrometric data (9a): Yellow crystal; mp 240-243 ˚C; IR (KBr): 3430, 3340 (NH₂), 1714 (CO), 2181 (CN) cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 1.16 (t, 3 H), 4.08 (q, 2 H), 5.03 (s, CH, 1 H), 6.56 (br s, NH₂, 2 H), 7.33-8.13 (m, 8 H, ArH); ^¹³C NMR (75 MHz, CDCl₃): δ = 14.2, 35.8, 60.2, 106.4, 113.1, 117.0, 122.3, 123.4, 124.3, 124.6, 129.5, 132.7, 146.7, 151.7, 152.7, 153.6, 158.0, 160.5, 168.2; LCMS (ESI): m/z = 408 [M⁺].

12

CCDC-784897 contains the supplementary crystallographic data for compound 10a. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.