A convenient synthetic method for preparing 2,5-disubstituted 1,6- methano[10]annulenes from 1,6-diacetylcyclohepta-1,3,5-triene

Bulletin of the Chemical Society of Japan

Volumn 73, Issue 7, 2000, Pages 1659-1671

  Kuroda, Shigeyasu ^a   Zuo, Shengli ^a   Oda, Mitsunori ^a   Fukuta, Atsushi ^a   Kajioka, Takanori ^a   Saito, Toyohiko ^a   Furuta, Shinji ^a   Tsukumo, Hitoshi ^a   Sano, Kenji ^a   Miyatake, Ryuta ^a   Tomoda, Shozo ^a   Hayakawa, Chiharu ^a   Nozawa, Haruna ^a  

^a UNIVERSITY OF TOYAMA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ANNULENE DERIVATIVE; CYCLOHEPTANE DERIVATIVE; REAGENT; TOLUENE;

ARTICLE; CATALYST; OXIDATION; REACTION ANALYSIS; REPRODUCIBILITY; STEREOCHEMISTRY; STEREOSPECIFICITY; SYNTHESIS;

EID: 0033928649     PISSN: 00092673     EISSN: None     Source Type: Journal    
DOI: 10.1246/bcsj.73.1659     Document Type: Article

References (48)

1. E. Vogel and H. D. Roth, Angew. Chem., Int. Ed. Engl., 3, 228 (1964).
2. E. Vogel, W. Klug, and A. Breuer, Org. Synth., Coll. Vol. 6, 731 (1987).
3. For recent reviews on annulenes, see: A. T. Balaban, M. Banciu, and V. Ciorba,"Annulenes, Benzo-, Hetero-, Homo-Derivatives and Their Valence Isomers," CRC Press, Baca Raton (1987), Vol. I; M. Nakagawa, "The Chemistry of Annulenes," Osaka University Press, Osaka (1996).
4. For recent reviews on annulenes, see: A. T. Balaban, M. Banciu, and V. Ciorba,"Annulenes, Benzo-, Hetero-, Homo-Derivatives and Their Valence Isomers," CRC Press, Baca Raton (1987), Vol. I; M. Nakagawa, "The Chemistry of Annulenes," Osaka University Press, Osaka (1996).
5. E. Vogel, W. A. Böll, and M. Biskup, Tetrahedron Lett., 1966, 1569; T. Scholl, J. Lex, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 920 (1982); R. Geiter, M. C. Böhm, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 922 (1982).
6. E. Vogel, W. A. Böll, and M. Biskup, Tetrahedron Lett., 1966, 1569; T. Scholl, J. Lex, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 920 (1982); R. Geiter, M. C. Böhm, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 922 (1982).
7. E. Vogel, W. A. Böll, and M. Biskup, Tetrahedron Lett., 1966, 1569; T. Scholl, J. Lex, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 920 (1982); R. Geiter, M. C. Böhm, and E. Vogel, Angew. Chem., Int. Ed. Engl., 21, 922 (1982).
8. H. Klenk, W.-D. Strohrer, and F. Effenberger, Chem. Ber., 109, 777 (1976).
9. K. Lammertsma and H. Cerfontain, J. Am. Chem. Soc., 100, 8244 (1978).
10. K. Takahashi, K. Ohnishi, and K. Takase, Chem. Lett., 1985, 1079.
11. E. Vogel, Pure Appl. Chem., 54, 1015 (1982).
12. B. M. Trost, Angew. Chem., Int. Ed. Engl., 34, 259 (1995).
13. Push-pull stabilized quinodimethanes of 1,6-methano[10]-annulene as p-conjugated organic materials were synthesized by Neidlein et al.; R. Neidlein and H. Zeiner, Chem. Ber., 115, 1409 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1285 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1333 (1982).
14. Push-pull stabilized quinodimethanes of 1,6-methano[10]-annulene as p-conjugated organic materials were synthesized by Neidlein et al.; R. Neidlein and H. Zeiner, Chem. Ber., 115, 1409 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1285 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1333 (1982).
15. Push-pull stabilized quinodimethanes of 1,6-methano[10]-annulene as p-conjugated organic materials were synthesized by Neidlein et al.; R. Neidlein and H. Zeiner, Chem. Ber., 115, 1409 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1285 (1982); R. Neidlein and H. Zeiner, Helv. Chim. Acta, 65, 1333 (1982).
16. All of the diols having asymmetric carbons were obtained as a mixture of meso-and dl-compounds. Repeated crystallization of the crude products of 5b - e gave the pure meso-diols, but the dl-diols were not obtained in pure form in any case so far.
17. N. Miyashita, A. Yoshikoshi, and P. A. Grieco, J. Org. Chem., 42, 3772 (1977).
18. M. Oda et al. reported that reactions of 1-(cyclohepta-1, 3,5-trien-1-yl)-1-phenylalkanols with acids, such as trifluoroacetic acid or zinc chloride, gave the cyclization products, dihydrobenz[a]-azulenes, as a major product. In the case of 1-(cyclohepta-1,3,5-trien-1-yl)-1-phenylpentanol, brief acid treatment gave the dehydration product in addition to cyclized dihydrobenz[a]azulenes. See: K. Mizumoto, K. Okada, and M. Oda, Tetrahedron Lett., 28, 2999 (1984).
19. By Effenberger et al. 4a had been synthesized as a mixture of 4a and 2,7-dimethyl derivative which has not been separated in pure form yet; see Ref. 5.
20. A similar synthetic approach for a synthesis of syn,syn-1, 6:8,17:10,15-trismethano[18]annulene with the corresponding divinyl compound and DDQ has already reported by Vogel et al. However, they could not clarified an dihydroannulene intermediate in thermal electrocyclization and any detail of the reactions and their application to preparation of other annulenes have not appeared yet: W. Wagemann, M. Iyoda, H. M. Deger, J. Sombroek, and E. Vogel, Angew. Chem., Int. Ed. Engl., 17, 956 (1978).
21. Although no change was observed on heating 8 in benzene without acid, reaction of 8 with DDQ in the absence of acid also gave 4, suggesting that 9 can also be dehydrogenated to produce 4. However, the yields of 4 by this method were found to be less than those under the conditions from 5 with acid except a case of a mixture of 8e and 9e, probably because of formation of byproducts which are assumed to be Diels-Alder type adducts between 8 and DDQ.
22. Synthesis of 8f by two different ways has already been reported: E. Vogel, U. H. Brinker, K. Nachtkamp, J. Wassen, and K. Müllen, Angew. Chem., Int. Ed. Engl., 12, 760 (1973); R. Okazaki, M. O-oka, N. Tokitoh, Y. Shishido, and N. Inamoto, Angew. Chem., Int. Ed. Engl., 20, 799 (1981).
23. Synthesis of 8f by two different ways has already been reported: E. Vogel, U. H. Brinker, K. Nachtkamp, J. Wassen, and K. Müllen, Angew. Chem., Int. Ed. Engl., 12, 760 (1973); R. Okazaki, M. O-oka, N. Tokitoh, Y. Shishido, and N. Inamoto, Angew. Chem., Int. Ed. Engl., 20, 799 (1981).
24. 1HNMR spectrum of this mixture shows the presence of 6f as a minor component; signals at δ - 0.21 (d, J = 8.0 Hz, 1H, H-11), 1.86 (m, 1H), 2.30-2.51 (m, 3H), 3.21 (d, J = 8.0 Hz, 1H, H-11), 5.35 (m, 1H, H-3), 6.12 (m, 2H), 6.23 (dd, J = 11.1, 2.9 Hz, 1H, H-2), 6.50 (m, 2H) for 6f were observed.
25. H. -R. Blattmann, W. A. Böll, E. Heilbronner, G. Bohlneicher, E. Vogel, and J. -P. Weber, Helv. Chim. Acta, 49, 127 (1966).
26. The signals at higher field were observed as a doublet (J = ca. 9 Hz) and another at lower field as a doublet of a triplet (J = ca. 9 and 1 Hz). The latter coupling with the small constant is best explained by a long-range coupling between the proton at the 11 position orientated to the substituents and those at the 6 and 10 positions with W-orientation. The signal assignment of the methylene protons is based on this observation. For other examples, see: J. Ojima, T. Kaimon, N. Hiraiwa, H. Higuchi, M. Ueno, and G. Yamamoto, J. Chem. Soc., Perkin Trans. 1, 1995, 2795.
27. A similar effect of electron-donating substituents on the chemical shift has already been observed. See Ref. 7.
28. The distance between the 1 and 6 positions of cycloheptatriene based on experimental data is reported to be 2.511 Å long: M. Traetterberg, J. Am. Chem. Soc., 86, 4265 (1964).
29. G. Büch and E. M. Burgess, J. Am. Chem. Soc., 84, 3104 (1962); A. P. t. Borg, H. Kloosterziel, and N. v. Neurs, Recl. Trav. Chim. Pays-Bas, 82, 717 (1963).
30. G. Büch and E. M. Burgess, J. Am. Chem. Soc., 84, 3104 (1962); A. P. t. Borg, H. Kloosterziel, and N. v. Neurs, Recl. Trav. Chim. Pays-Bas, 82, 717 (1963).
31. J. A. Berson and M. R. Willcot, III, J. Am. Chem. Soc., 87, 2751 and 2752 (1965); J. A. Berson and M. R. Willcot, III, J. Am. Chem. Soc., 86, 2494 (1966).
32. J. A. Berson and M. R. Willcot, III, J. Am. Chem. Soc., 87, 2751 and 2752 (1965); J. A. Berson and M. R. Willcot, III, J. Am. Chem. Soc., 86, 2494 (1966).
33. J. J. P. Stewart, J. Comput. Chem., 10, 209 (1989).
34. Although there were generated many geometrical isomers of 8b in terms of rotation around the single bond between the cycloheptatriene and the substituent styryl group by the calculations, we only evaluated the isomer which leads to the products.
35. All TSs show an imaginary vibrational frequency and proper vectors.
36. W. R. Roth, M. Bohm, and H. -W. Lennartz, Angew. Chem., Int. Ed. Engl., 22, 1007 (1983); M. Schulman, R. L. Disch, and M. L. Sabio, J. Am. Chem. Soc., 106, 7696 (1984); C. S. Q. Lew, T. -H. Tang, I. G. Csizmadia, and B. Capon, J. Chem. Soc., Chem. Commun., 1995, 175.
37. W. R. Roth, M. Bohm, and H. -W. Lennartz, Angew. Chem., Int. Ed. Engl., 22, 1007 (1983); M. Schulman, R. L. Disch, and M. L. Sabio, J. Am. Chem. Soc., 106, 7696 (1984); C. S. Q. Lew, T. -H. Tang, I. G. Csizmadia, and B. Capon, J. Chem. Soc., Chem. Commun., 1995, 175.
38. W. R. Roth, M. Bohm, and H. -W. Lennartz, Angew. Chem., Int. Ed. Engl., 22, 1007 (1983); M. Schulman, R. L. Disch, and M. L. Sabio, J. Am. Chem. Soc., 106, 7696 (1984); C. S. Q. Lew, T. -H. Tang, I. G. Csizmadia, and B. Capon, J. Chem. Soc., Chem. Commun., 1995, 175.
39. -1; M. B. Rubin, J. Am. Chem. Soc., 103, 7791 (1981).
40. -1, respectively.
41. R. B. Woodward and R. Hoffmann, "The Conservation of Orbital Symmetry," Academic Press, New York (1969).
42. The top side of p-orbital array means the side to which the methano bridge stands up and the bottom is the opposite side.
43. Calculated total energies (in a.u.) of 9b, 6b, and 6b′ by the BLYP/3-21G* calculations are as follows: -883.853010 for 9b, -883.863364 for 6b, and -883.861240 for 6b′.
44. D. B. Ledlie, T. Swan, J. Pile, and L. Bowers, J. Org. Chem., 41, 419 (1976); K. Lammertsma and H. Cerfortain, J. Am. Chem. Soc., 102, 4528 (1980); E. Vogel, T. Scholl, J. Lex, and G. Hohlneicher, Angew. Chem., Int. Ed. Engl., 21, 869 (1982).
45. D. B. Ledlie, T. Swan, J. Pile, and L. Bowers, J. Org. Chem., 41, 419 (1976); K. Lammertsma and H. Cerfortain, J. Am. Chem. Soc., 102, 4528 (1980); E. Vogel, T. Scholl, J. Lex, and G. Hohlneicher, Angew. Chem., Int. Ed. Engl., 21, 869 (1982).
46. D. B. Ledlie, T. Swan, J. Pile, and L. Bowers, J. Org. Chem., 41, 419 (1976); K. Lammertsma and H. Cerfortain, J. Am. Chem. Soc., 102, 4528 (1980); E. Vogel, T. Scholl, J. Lex, and G. Hohlneicher, Angew. Chem., Int. Ed. Engl., 21, 869 (1982).
47. E. Vogel, H. M. Deger, J. Sombroek, J. Palm, A. Wagner, and J. Lex, Angew. Chem., Int. Ed. Engl., 19, 41 (1980).
48. H. Higuchi, M. Kondo, H. Yoneyama, J. Ojima, and M. Iyoda, Bull. Chem. Soc. Jpn., 66, 275 (1993).