Synlett 2012; 23(17): 2544-2548
© Georg Thieme Verlag Stuttgart · New York
Anodic Cyclization of 1,7-Diarylheptane-1,7-diones to the Corresponding 1,2-Diaroylcyclopentanes
Mitsuhiro Okimoto*
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
,
Haruki Yamamori
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
,
Kousuke Ohashi
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
,
Shinnosuke Nishikawa
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
,
Masayuki Hoshi
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
,
Takashi Yoshida
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Kitami, Koen-cho, Hokkaido 090-8507, Japan Fax: +81(157)247719 eMail:
okimotmt@mail.kitami-it.ac.jp
› Institutsangaben
Abstract
A range of 1,7-diarylheptane-1,7-diones were electrooxidized in the presence of iodide ions and a base in a mixture of methanol and toluene as the reaction solvents to give the corresponding cyclized 1,2-diaroylcyclopentanes in moderate to good yields. The reactions were carried out under extremely mild reaction conditions for which the optimal amount of electrolytic current varied from 2.05–3.17 F·mol–1 depending on the substrates. The reaction presumably proceeds through a two-electron oxidation process in which the iodide ion plays an important role as the electron carrier.
Key words electron transfer - oxidation - cyclization - ring closure - green chemistry - iodine
References
See for example:
1a Longchamp MS, Caullet C, Libert M. Bull. Soc. Chim. Fr. 1974; 353
1b Nilsson A, Palmquist U, Ronlán A, Parker VD. J. Am. Chem. Soc. 1975; 97: 3540
1c Sainsbury M, Watt J. J. Chem. Soc., Perkin Trans. 1 1979; 108
1d Andreades S, Zahnow EW. J. Am. Chem. Soc. 1969; 91: 4181
1e Nilsson A, Rolan A, Park VD. Tetrahedron Lett. 1975; 1107
1f Richard JA, Evans DH. J. Electroanal. Chem. 1977; 81: 171
1g Nyberg K. Acta Chem. Scand. 1973; 27: 503
1h Yoshida K, Fueno T. J. Org. Chem. 1972; 37: 4145
1i Miyashi T, Nishizawa Y, Sugiyama T, Mukai T. J. Am. Chem. Soc. 1977; 99: 6111
1j Chiba T, Takata Y. J. Org. Chem. 1977; 42: 2973
1k Yoshida K, Fueno T. J. Org. Chem. 1971; 36: 1523
1l Chiba K, Arakawa T, Tada M. Chem. Commun. 1996; 1763
1m Chiba K, Jinno M, Nozaki A, Tada M. Chem. Commun. 1997; 1403
1n Fry AJ, Porter JM, Fry PF. J. Org. Chem. 1996; 61: 3191
1o Mizuno K, Ichinose N, Otsuji Y. J. Org. Chem. 1992; 57: 1855
1p Shundo R, Nishiguch I, Matsubara Y, Hirashima T. Tetrahedron 1991; 47: 831
1q Suga S, Okajima M, Yoshida J. Tetrahedron Lett. 2001; 42: 2173
1r Suga S, Suzuki S, Yamamoto A, Yoshida J. J. Am. Chem. Soc. 2000; 122: 10244
1s Yoshida J, Suga S, Suzuki S, Kinomura N, Yamamoto A, Fujiwara K. J. Am. Chem. Soc. 1999; 121: 9546
1t Matsumoto K, Fuji S, Ueoka K, Suga S, Yoshida J. Angew. Chem. Int. Ed. 2008; 47: 2506
1u Nokami T, Ohata K, Inoue M, Tsuyama H, Shibuya A, Soga K, Okajima M, Suga S, Yoshida J. J. Am. Chem. Soc. 2008; 130: 10864
1v Kanada Y, Onomura O, Maki T, Matsumura Y. Chirality 2003; 15: 89
1w Libendi SS, Demizu Y, Onomura O. Org. Biomol. Chem. 2009; 7: 351
2a Chiba T, Okimoto M, Nagai H, Takata Y. J. Org. Chem. 1979; 44: 3519
2b Okimoto M, Chiba T. J. Org. Chem. 1990; 55: 1070
2c Chiba T, Okimoto M. J. Org. Chem. 1992; 57: 1375
2d Chiba T, Okimoto M. Chem. Lett. 1993; 22: 521
2e Okimoto M, Takahashi Y. Synthesis 2002; 2215
2f Okimoto M, Numata K, Takahashi Y, Hoshi M, Tomozawa K, Shigemoto T. Synlett 2005; 2507
2g Okimoto M, Yoshida T, Hoshi M, Hattori K, Komata M, Numata K, Tomozawa K. Synlett 2006; 1753
3a Gao JY, Chen WX, Jiang K. Acta Chim. Sinica 1982; 40: 91
3b Baumstark AL, McCloskey CJ, Witt KE. J. Org. Chem. 1978; 43: 3609
3c Gong YD, Tanaka H, Iwasawa N, Narasaka K. Bull. Chem. Soc. Jpn. 1998; 71: 2181
3d Nakamura M, Miki M, Majima T. J. Chem. Soc., Perkin Trans. 1 2000; 415
4 Okimoto, M.; Takahashi, Y.; Kakuchi, T. Bull. Chem. Soc. Jpn. 2003 , 76, 207; Note: At present, cyclobutane and cyclohexane derivatives could not be obtained from the corresponding aromatic diketones by the electrooxidation method.
5 1,7-Diarylheptane-1,7-diones were prepared by using standard Friedel–Crafts acylation conditions between pimeloyl dichloride and aromatic compounds in the presence of AlCl3 .6 Preparative-scale electrooxidations were carried out in a tall 50-mL beaker equipped with a cylindrical fine frit cup (height: 45 mm, diameter: 12 mm) as the cathode compartment with a nickel coil cathode (length: 280 mm, diameter: 1 mm), along with a cylindrical platinum net anode (height: 35 mm, diameter: 30 mm, 50 mesh).Typical Procedure : A solution of 1,7-diphenylheptane-1,7-dione 1a (1.40 g, 5 mmol) in a mixture of MeOH (25 mL) and toluene (15 mL) containing KI (0.83 g, 5.0 mmol) and NaOMe (2.70 g, 5.0 mmol) was electrooxidized under a constant current (0.3 A) at r.t. (ca. 15 °C) with magnetic stirring. During the course of the electrooxidation, the composition of the reaction mixture was monitored by GC and/or TLC analyses. Passage of the electric current was continued until the increase in the amount of the product was no longer detected (2.24 F·mol–1 ). The reaction mixture was concentrated in vacuo at approximately 60 °C to near dryness. The resulting residue was treated with brine (ca. 30 mL), then extracted with diethyl ether or chloroform (3 × 40 mL), and dried overnight over sodium sulfate. After removal of the solvent in vacuo, the crude product was purified by silica gel column chromatography (height: 350 mm, diameter: 25 mm) using dichloromethane as the eluent, to afford the pure cyclized product 2a (0.88 g, 63%). The electrooxidation products were characterized by using IR, 1 H and 13 C NMR analyses, and by HRMS. Cyclopentane-1,2-diylbis(phenylmethanone) (2a): Yield: 0.88 g (63%); colorless, fine cubic crystals; mp 88–89 °C (MeOH); Rf
= 0.64 (CH2 Cl2 ). IR (KBr): 3061 (w), 2965, 1675 (s), 1595, 1450, 1322, 1284, 1194, 987, 781, 702 (s) cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.75–1.92 (m, 4 H, 2 × CH2 ), 2.18–2.31 (m, 2 H, CH2 ), 4.38–4.46 (m, 2 H, 2 × CH), 7.45–7.57 (m, 6 H, 6 × CH), 7.97–8.03 (m, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 26.29 (CH2 ), 32.06 (CH2 ), 48.67 (CH), 128.58 (CH), 128.68 (CH), 133.06 (CH), 136.41 (C), 201.74 (CO). MS (EI, 70 eV): m /z (%) = 278 (6) [M+ ], 260 (7), 174 (25), 173 (98) [M+ – C6 H5 CO], 106 (19), 105 (100) [C6 H5 CO], 95 (10), 77 (61) [C6 H5 ], 67 (7), 51 (15). HRMS: m /z [M+ ] calcd for C19 H18 O2 : 278.1307; found: 278.1310. Cyclopentane-1,2-diylbis(p -tolylmethanone) (2b): Yield: 1.06 g (69%); colorless, column crystals; mp 92–93 °C (MeOH); Rf
= 0.65 (CH2 Cl2 ). IR (KBr): 3066 (w), 2949, 1667 (s), 1607 (s), 1412, 1335, 1222, 1178, 1016, 843, 825 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.75–1.89 (m, 4 H, 2 × CH2 ), 2.15–2.27 (m, 2 H, CH2 ), 2.38 (s, 6 H, 2 × CH3 ), 4.34–4.42 (m, 2 H, 2 × CH), 7.22 (d, J = 8 Hz, 4 H, 4 × CH), 7.90 (d, J = 8 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 21.59 (CH3 ), 26.32 (CH2 ), 32.14 (CH2 ), 48.56 (CH), 128.81 (CH), 129.25 (CH), 133.93 (C), 143.79 (C), 201.42 (CO). MS (EI, 70 eV): m /z (%) = 306 (4) [M+ ], 289 (8), 288 (35), 188 (27), 187 (86) [M+ – CH3 C6 H4 CO], 120 (30), 119 (100) [CH3 C6 H4 CO], 95 (13), 91 (70), [CH3 C6 H4 ], 65 (29). HRMS: m /z [M+ ] calcd for C21 H22 O2 : 306.1619; found: 306.1602. Cyclopentane-1,2-diylbis[(4-ethylphenyl)methanone] (2c): Yield: 1.10 g (66%); colorless, cubic crystals; mp 56–57 °C (MeOH); Rf
= 0.72 (CH2 Cl2 ). IR (KBr): 3057 (w), 2966, 2933, 1665 (s), 1606 (s), 1416, 1330, 1218, 1181, 1006, 848 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.23 (t, J = 8 Hz, 6 H, 2 × CH3 ), 1.76–1.91 (m, 4 H, 2 × CH2 ), 2.18–2.28 (m, 2 H, CH2 ), 2.67 (q, J = 8 Hz, 4 H, 2 × CH2 ), 4.35–4.43 (m, 2 H, 2 × CH), 7.26 (d, J = 8 Hz, 4 H, 4 × CH), 7.93 (d, J = 8 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ= 15.16 (CH3 ), 26.33 (CH2 ), 28.91 (CH2 ), 32.15 (CH2 ), 48.61 (CH), 128.07 (CH), 128.94 (CH), 134.16 (C), 149.96 (C), 201.47 (CO). MS (EI, 70 eV): m /z (%) = 334 (3) [M+ ], 316 (15), 202 (22), 201 (76) [M+ – CH3 CH2 C6 H4 CO], 134 (23), 133 (100) [CH3 CH2 C6 H4 CO], 105 (26) [CH3 CH2 C6 H4 ], 103 (13), 79 (19), 77 (13). HRMS: m /z [M+ ] calcd for C23 H26 O2 : 334.1933; found: 334.1937. Cyclopentane-1,2-diylbis[(4-methoxyphenyl)methanone] (2d): Yield: 1.30 g (77%); colorless, fine cubic crystals; mp 130–131 °C (MeOH); Rf
= 0.43 (CH2 Cl2 ). IR (KBr): 3013 (w), 2959, 1665 (s), 1600 (s), 1575, 1331, 1261, 1215, 1166 (s), 1018, 1004, 838 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.76–1.91 (m, 4 H, 2 × CH2 ), 2.15–2.27 (m, 2 H, CH2 ), 3.85 (s, 6 H, 2 × CH3 O), 4.30–4.38 (m, 2 H, 2 × CH), 6.91 (d, J = 9 Hz, 4 H, 4 × CH), 7.98 (d, J = 9 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 26.39 (CH2 ), 32.28 (CH2 ), 48.46 (CH), 55.45 (OCH3 ), 113.72 (CH), 129.48 (C), 130.98 (CH), 163.46 (C), 200.50 (CO). MS (EI, 70 eV): m /z (%) = 338 (2) [M+ ], 320 (7), 204 (9), 203 (66) [M+ – CH3 OC6 H4 CO], 136 (11), 135 (100) [CH3 OC6 H4 CO], 118 (4), 107 (10) [CH3 OC6 H4 ], 92 (8), 77 (11). HRMS: m /z [M+ ] calcd for C21 H22 O4 : 338.1518; found: 338.1473.Cyclopentane-1,2-diylbis[(4-ethoxyphenyl)methanone] (2e): Yield: 1.17 g (64%); colorless, cubic crystals; mp 109–110 °C (MeOH); Rf
= 0.49 (CH2 Cl2 ). IR (KBr): 3075 (w), 2930, 1662 (s), 1600 (s), 1573, 1509, 1321, 1260, 1190, 1169 (s), 1038, 846 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.42 (t, J = 7 Hz, 6 H, 2 × CH3 ), 1.76–1.90 (m, 4 H, 2 × CH2 ), 2.16–2.26 (m, 2 H, CH2 ), 4.07 (q, J = 7 Hz, 4 H, 2 × CH2 O), 4.30–4.38 (m, 2 H, 2 × CH), 6.88 (d, J = 9 Hz, 4 H, 4 × CH), 7.97 (d, J = 9 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 14.65 (CH3 ), 26.39 (CH2 ), 32.28 (CH2 ), 48.44 (CH), 63.70 (OCH2 ), 114.14 (CH), 129.30 (C), 130.97 (CH), 162.89 (C), 200.50 (CO). MS (EI, 70 eV): m /z (%) = 366 (2) [M+ ], 348 (15), 319 (13), 218 (15), 217 (85) [M+ – CH3 CH2 OC6 H4 CO], 150 (15), 149 (100) [CH3 CH2 OC6 H4 CO], 121 (55) [CH3 CH2 OC6 H4 ], 93 (13), 65 (8). HRMS: m /z [M+ ] calcd for C23 H26 O4 : 366.1831; found: 366.1824. Cyclopentane-1,2-diylbis[(4-fluorophenyl)methanone] (2f): Yield: 1.05 g (67%); colorless, fine cubic crystals; mp 84–86 °C (MeOH); Rf
= 0.69 (CH2 Cl2 ). IR (KBr): 3060 (w), 2960, 1672 (s), 1596 (s), 1504, 1320, 1303, 1231 (s), 1205, 1150, 1007, 853 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.75–1.90 (m, 4 H, 2 × CH2 ), 2.16–2.31 (m, 2 H, CH2 ), 4.30–4.39 (m, 2 H, 2 × CH), 7.06–7.16 (m, 4 H, 4 × CH), 7.99–8.07 (m, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 26.29 (CH2 ), 32.08 (CH2 ), 48.70 (CH), 115.74 (d, J
C–F = 21 Hz, CH), 131.35 (d, J
C–F = 10 Hz, CH), 132.80 (d, J
C–F = 3 Hz, C), 165.79 (d, J
C–F = 254 Hz, C), 200.09 (CO). MS (EI, 70 eV): m /z (%) = 314 (3) [M+ ], 192 (21), 191 (76) [M+ – FC6 H4 CO], 164 (7), 124 (22), 123 (100) [FC6 H4 CO], 96 (7), 95 (54) [FC6 H4 ], 75 (19), 67 (9). HRMS: m /z [M+ ] calcd for C19 H16 O2 F2 : 314.1118; found: 314.1167. Cyclopentane-1,2-diylbis[(4-chlorophenyl)methanone] (2g): Yield: 1.12 g (64%); colorless, fine needle-like crystals; mp 97–99 °C (MeOH); Rf
= 0.75 (CH2 Cl2 ). IR (KBr): 3062 (w), 2950, 1666 (s), 1588 (s), 1568, 1400, 1331, 1211 (s), 1089, 1005, 848, 839 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.76–1.88 (m, 4 H, 2 × CH2 ), 2.16–2.30 (m, 2 H, CH2 ), 4.30–4.38 (m, 2 H, 2 × CH), 7.42 (d, J = 9 Hz, 4 H, 4 × CH), 7.93 (d, J = 9 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 26.24 (CH2 ), 31.98 (CH2 ), 48.66 (CH), 128.93 (CH), 130.09 (CH), 134.63 (C), 139.60 (C), 200.33 (CO). MS (EI, 70 eV): m /z (%) = 350 (< 1) [M+ , 37 Cl2 ], 348 (2) [M+ , 37 Cl, 35 Cl], 346 (3) [M+ , 35 Cl2 ],
209 (32) [M+ – ClC6 H4 CO], 208 (15), 207 (83) [M+ – ClC6 H4 CO], 141 (35) [37 ClC6 H4 CO], 140 (12), 139 (100) [35 ClC6 H4 CO], 113 (12) [37 ClC6 H4 ], 111 (35) [35 ClC6 H4 ]. HRMS: m /z [M+ ] calcd for C19 H16 O2
37 Cl2 : 350.0468; found: 350.0462. HRMS: m /z [M+ ] calcd for C19 H16 O2
35 Cl/37 Cl: 348.0498; found: 348.0438. HRMS: m /z [M+ ] calcd for C19 H16 O2
35 Cl2 : 346.0527; found: 346.0577. Cyclopentane-1,2-diylbis[(4-bromophenyl)methanone] (2h): Yield: 1.51 g (69%); colorless, fine needle-like crystals; mp 107–109 °C (MeOH); Rf
= 0.75 (CH2 Cl2 ). IR (KBr): 3069 (w), 2946, 1666 (s), 1584 (s), 1565, 1397, 1330, 1210 (s), 1068, 1004, 844, 837 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ= 1.73–1.87 (m, 4 H, 2 × CH2 ), 2.16–2.30 (m, 2 H, CH2 ), 4.30–4.37 (m, 2 H, 2 × CH), 7.59 (d, J = 9 Hz, 4 H, 4 × CH), 7.86 (d, J = 9 Hz, 4 H, 4 × CH). 13 C NMR (100 MHz, CDCl3 ): δ= 26.22 (CH2 ), 31.94 (CH2 ), 48.59 (CH), 128.36 (C), 130.18 (CH), 131.91 (CH), 134.98 (C), 200.51 (CO). MS (EI, 70 eV): m /z (%) = 438 (1) [M+ , 81 Br2 ], 436 (2) [M+ , 81 Br, 79 Br], 434 (1) [M+ , 79 Br2 ], 253 (89) [M+ – BrC6 H4 CO], 251 (90) [M+ – BrC6 H4 CO], 185 (99) [81 BrC6 H4 CO], 183 (100) [79 BrC6 H4 CO], 157 (32) [81 BrC6 H4 ], 155 (31) [79 BrC6 H4 ], 76 (11). HRMS: m /z [M+ ] calcd for C19 H16 O2
81 Br2 : 437.9476; found: 437.9411. HRMS: m /z [M+ ] calcd for C19 H16 O2
81 Br/79 Br: 435.9497; found: 435.9491. HRMS: m /z [M+ ] calcd for C19 H16 O2
79 Br2 : 433.9517; found: 433.9495. Cyclopentane-1,2-diylbis[(2,5-dimethylphenyl)-methanone] (2i): Yield: 1.09 g (65%); slightly yellowish viscous oily liquid; bp 206–208 °C/1.2 mbar; Rf
= 0.72 (CH2 Cl2 ). IR (neat): 3020 (w), 2959 (s), 2926, 1678, 1495, 1449, 1294, 1244, 1169, 1006, 817 cm–1 . 1 H NMR (400 MHz, CDCl3 ): δ = 1.71–1.84 (m, 4 H, 2 × CH2 ), 2.02–2.14 (m, 2 H, CH2 ), 2.32 (s, 6 H, 2 × CH3 ), 2.38 (s, 6 H, 2 × CH3 ), 4.16–4.25 (m, 2 H, 2 × CH), 7.03–7.17 (m, 4 H, 4 × CH), 7.36–7.41 (m, 2 H, 2 × CH). 13 C NMR (100 MHz, CDCl3 ): δ = 20.45 (CH3 ), 20.91 (CH3 ), 26.02 (CH2 ), 31.14 (CH2 ), 51.62 (CH), 128.96 (CH), 131.53 (CH), 131.71 (CH), 134.63 (C), 135.19 (C), 138.08 (C), 206.06 (CO). MS (EI, 70 eV): m /z (%) = 334 (7) [M+ ], 265 (12), 201 (36) [M+ – (CH3 )2 C6 H3 CO], 134 (24), 133 (100) [(CH3 )2 C6 H3 CO], 105 (44) [(CH3 )2 C6 H3 ], 103 (19), 95 (7), 79 (24), 77 (22). HRMS: m /z [M+ ] calcd for C23 H26 O2 : 334.1933; found: 334.1904
6 Fuson RC, Walker JT.
Org. Synth. Coll. Vol. II
. John Wiley & Sons; New York: 1943: 169
