A Convenient Synthesis of Highly Substituted Furans by Microwave Irradiation of Ring-Fused Alkylidenecyclopropanes

Abstract

Microwave irradiation of ring-fused alkylidenecyclopropanes under solvent-free conditions afforded highly substituted furans in good yields.

Key words

microwave reaction - solvent-free - substituted furan - ring-fused alkylidenecyclopropane - bicyclo[4.1.0]heptane derivative

References

• 1a Dean FM. In Advances in Heterocyclic Chemistry   Vol. 30:  Katritzky AR. Academic Press; New York: 1982.  p.167-238  
• 1b Keay BA. Dibble PW. In Comprehensive Heterocyclic Chemistry II   Vol. 2:  Bird CW. Elsevier; New York: 1996.  p.395-436  ; and references cited therein
• 2 Lipshutz BH. Chem. Rev.  1986,  86:  795 
• 3 Hou XL. Cheung HY. Hon TY. Kwan PL. Lo TH. Tong SY. Wong HNC. Tetrahedron  1998,  54:  1955 ; and references cited therein
• 4 Keay BA. Chem. Soc. Rev.  1999,  28:  209 ; and references therein
• 5a Lee YR. Suk JY. Kim BS. Org. Lett.  2000,  2:  1387 
• 5b Nishibayashi Y. Yoshikawa M. Inada Y. Milton MD. Hidai M. Uemura S. Angew. Chem. Int. Ed.  2003,  42:  2681 
• 5c Rao HSP. Jothilingam S. J. Org. Chem.  2003,  68:  5392 
• 6 Goldschmidt Z. Mauda S. Tetrahedron Lett.  1976,  4183 
• 7a Lidström P. Tierney J. Wathey B. Westman J. Tetrahedron  2001,  57:  9225 
• 7b Perreux L. Loupy A. Tetrahedron  2001,  57:  9199 
• 7c Larhed M. Moberg C. Hallberg A. Acc. Chem. Res.  2002,  35:  717 
• 7d Nüchter M. Ondruschka B. Jungnickel A. Müller U. J. Phys. Org. Chem.  2000,  13:  579 
• 8a Loupy A. Petit A. Hamelin J. Texier-Boullet F. Jacquault P. Mathé D. Synthesis  1998,  1213 
• 8b Kabalka GW. Wang L. Namboodiri V. Pagni RM. Tetrahedron Lett.  2000,  41:  5151 
• 8c Kabalka GW. Wang L. Pagni RM. Tetrahedron  2001,  57:  8017 
• 8d Varma RS. Namboodiri VV. Pure Appl. Chem.  2001,  73:  1309 
• 9 Brandi A. Goti A. Chem. Rev.  1998,  98:  589 ; and references cited therein
• 10 Suginome M. Matsuda T. Ito Y. J. Am. Chem. Soc.  2000,  122:  11015 
• 11 Ishiyama T. Momota S. Miyaura N. Synlett  1999,  1790 
• 12 Lautens M. Meyer C. Lorenz A. J. Am. Chem. Soc.  1996,  118:  10676 
• 13a Nakamura I. Oh BH. Saito S. Yamamoto Y. Angew. Chem. Int. Ed.  2001,  40:  1298 
• 13b Camacho DH. Nakamura I. Saito S. Yamamoto Y. J. Org. Chem.  2001,  66:  270 
• 13c Nakamura I. Saito S. Yamamoto Y. J. Am. Chem. Soc.  2000,  122:  2661 ; and references cited therein
• 14 Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev.  2003,  103:  1213 
• 15 Chowdhury MA. Senboku H. Tokuda M. Masuda Y. Chiba T. Tetrahedron Lett.  2001,  42:  7075 
• 16a Chowdhury MA. Senboku H. Tokuda M. Tetrahedron Lett.  2003,  44:  3329 
• 16b Chowdhury MA. Senboku H. Tokuda M. Tetrahedron  2004,  60:  475 
• 17 Chowdhury MA. Senboku H. Tokuda M. Chiba T. Tetrahedron  2002,  58:  1673 
• 18 Kaboudin B. Norouzi H. Tetrahedron Lett.  2004,  45:  1283 ; and reference cited therein
• 19 Williams L. Chem. Commun.  2000,  435 
• 20 Álvarez-Toledano C. Aguilar-Pacheco R. Baldovino-Pantaleón O. Gutiérrez-Pérez R. Miranda-Ruvalcaba R. Penieres-Carrillo G. J. Mol. Catal. A: Chem.  2000,  164:  85 
• 22 An analogous method of this type was reported by: Iwanoff C. Chem. Ber.  1954,  87:  1600 

21

General procedure for microwave reaction is as follows: Alkylidenecyclopropane 1 (300 mg) was taken in a ground-joint test-tube with a stir bar. It was placed in the microwave oven and equipped with a condenser. Simple microwave reaction apparatus, Model No. SMW-05, 650 W, Shikoku Keisoku Kogyo Co. Ltd., Japan, was used. Irradiation was carried out with stirring for 5 min. After cooling to r.t., the product was purified by column chromatography on silica gel, eluting with n-hexane to give pure products. All new products were characterized fully by ¹H NMR, ¹³C NMR and HRMS or elemental analyses.
Selected data of 3-methyl-2-phenyl-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan (2d): ¹H NMR (270 MHz, CDCl₃): δ = 1.65-1.85 (m, 6 H), 2.13 (s, 3 H), 2.41 (t, J = 5.9 Hz, 2 H), 2.80 (t, J = 5.9 Hz, 2 H), 7.18 (t, J = 7.6 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 2 H), 7.57 (d, J = 8.3 Hz, 2 H). ¹³C NMR (67.5 MHz): δ = 9.83, 23.67, 26.53, 28.49, 28.93, 30.82, 117.32, 123.24, 125.11, 125.94, 128.35, 132.26, 145.14, 152.22. EIMS: m/z (rel. intensity) = 226 (100) [M⁺], 211 (11), 197 (18), 184 (11), 172 (28), 155 (6), 141 (6), 105 (7), 77 (8). HRMS: m/z calcd for C₁₆H₁₈O: 226.1358. Found: 226.1351.
Selected data of 3-methyl-2-phenyl-4,5,6,7,8,9-hexahydrocycloocta[b]furan (4d): ¹H NMR (270 MHz, CDCl₃): δ = 1.40-1.60 (m, 4 H), 1.60-1.80 (m, 4 H), 2.14 (s, 3 H), 2.50 (t, J = 6.3 Hz, 2 H), 2.79 (t, J = 6.3 Hz, 2 H), 7.18 (t, J = 7.6 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 2 H), 7.59 (d, J = 7.3 Hz, 2 H). ¹³C NMR (67.5 MHz): δ = 9.70, 21.53, 25.60, 25.81, 26.15, 27.97, 28.21, 116.92, 120.97, 124.89, 125.83, 128.35, 132.38, 145.76, 150.61. EIMS: m/z (rel. intensity) = 240 (100) [M⁺], 212 (58), 197 (30), 185 (42), 172 (23), 155 (11), 141 (14), 105 (21), 77 (26). HRMS: m/z calcd for C₁₇H₂₀O: 240.1514. Found: 240.1511. Anal. Calcd for C₁₇H₂₀O: C, 84.96; H, 8.39. Found: C, 85.02; H, 8.39.