Facial selectivities of benzofluorenes bearing a carbonyl, an olefin, or a diene group in spiro geometry. π Spiro substituent effects

Tetrahedron Letters

Volumn 39, Issue 5-6, 1998, Pages 403-406

  Tsuji, Motonori ^a   Ohwada, Tomohiko ^a   Shudo, Koichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

FLUORENE DERIVATIVE; SPIRO COMPOUND;

ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

BETULACEAE;

EID: 0032576852     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10560-3     Document Type: Article

References (27)

1. 1) Ohwada, T., J. Am. Chem. Soc., 1992, 114, 8818-8827. Ohwada, T.; Shudo, K., Chem. Pharm. Bull., 1991, 39, 2176-2178.
2. 1) Ohwada, T., J. Am. Chem. Soc., 1992, 114, 8818-8827. Ohwada, T.; Shudo, K., Chem. Pharm. Bull., 1991, 39, 2176-2178.
3. 2) Simmons, H. E.; Fukunaga, T., J. Am. Chem. Soc., 1967, 89, 5208-5215. Gordon, M. D.; Fukunaga, T.; and Simmons, H. E., J. Am. Chem. Soc., 1976, 98, 8401-8407. Dürr, H; Gleiter, R., Angew. Chem. Int. Ed. Engl., 1978, 17, 559-569.
4. 2) Simmons, H. E.; Fukunaga, T., J. Am. Chem. Soc., 1967, 89, 5208-5215. Gordon, M. D.; Fukunaga, T.; and Simmons, H. E., J. Am. Chem. Soc., 1976, 98, 8401-8407. Dürr, H; Gleiter, R., Angew. Chem. Int. Ed. Engl., 1978, 17, 559-569.
5. 2) Simmons, H. E.; Fukunaga, T., J. Am. Chem. Soc., 1967, 89, 5208-5215. Gordon, M. D.; Fukunaga, T.; and Simmons, H. E., J. Am. Chem. Soc., 1976, 98, 8401-8407. Dürr, H; Gleiter, R., Angew. Chem. Int. Ed. Engl., 1978, 17, 559-569.
6. 3) Benzo[b]fluorenes bearing the spiro substituents (1b and 2b) were prepared as described in Thiele, J.; Schneider, J. Liebigs Ann. Chem., 1909, 350, 287-299. Both benzo[a]-(1a and 2a) and benzo[c]fluorenes (1c and 2c) were prepared as described in Hopkinson, A. C.; Lee-Ruff, E.; Maleki, M., Synthesis, 1986, 366-371. Both 3b and 3c were prepared from the corresponding olefins (2b and 2c) as described in Müller, H.; Herberich, G. E. Chem. Ber., 1971, 104, 2772 -2780. 2d was prepared by McMurry reaction of the corresponding dimethyl ketone as described in McMurry, J. E.; Lectka, T.; Rico, J. G. J. Org. Chem., 1989, 54, 3748-3749. See also reference 1. All new compounds gave satisfactory NMR data and either combustion analysis or HRMS data.
7. 3) Benzo[b]fluorenes bearing the spiro substituents (1b and 2b) were prepared as described in Thiele, J.; Schneider, J. Liebigs Ann. Chem., 1909, 350, 287-299. Both benzo[a]-(1a and 2a) and benzo[c]fluorenes (1c and 2c) were prepared as described in Hopkinson, A. C.; Lee-Ruff, E.; Maleki, M., Synthesis, 1986, 366-371. Both 3b and 3c were prepared from the corresponding olefins (2b and 2c) as described in Müller, H.; Herberich, G. E. Chem. Ber., 1971, 104, 2772 -2780. 2d was prepared by McMurry reaction of the corresponding dimethyl ketone as described in McMurry, J. E.; Lectka, T.; Rico, J. G. J. Org. Chem., 1989, 54, 3748-3749. See also reference 1. All new compounds gave satisfactory NMR data and either combustion analysis or HRMS data.
8. 3) Benzo[b]fluorenes bearing the spiro substituents (1b and 2b) were prepared as described in Thiele, J.; Schneider, J. Liebigs Ann. Chem., 1909, 350, 287-299. Both benzo[a]-(1a and 2a) and benzo[c]fluorenes (1c and 2c) were prepared as described in Hopkinson, A. C.; Lee-Ruff, E.; Maleki, M., Synthesis, 1986, 366-371. Both 3b and 3c were prepared from the corresponding olefins (2b and 2c) as described in Müller, H.; Herberich, G. E. Chem. Ber., 1971, 104, 2772 -2780. 2d was prepared by McMurry reaction of the corresponding dimethyl ketone as described in McMurry, J. E.; Lectka, T.; Rico, J. G. J. Org. Chem., 1989, 54, 3748-3749. See also reference 1. All new compounds gave satisfactory NMR data and either combustion analysis or HRMS data.
9. 3) Benzo[b]fluorenes bearing the spiro substituents (1b and 2b) were prepared as described in Thiele, J.; Schneider, J. Liebigs Ann. Chem., 1909, 350, 287-299. Both benzo[a]-(1a and 2a) and benzo[c]fluorenes (1c and 2c) were prepared as described in Hopkinson, A. C.; Lee-Ruff, E.; Maleki, M., Synthesis, 1986, 366-371. Both 3b and 3c were prepared from the corresponding olefins (2b and 2c) as described in Müller, H.; Herberich, G. E. Chem. Ber., 1971, 104, 2772 -2780. 2d was prepared by McMurry reaction of the corresponding dimethyl ketone as described in McMurry, J. E.; Lectka, T.; Rico, J. G. J. Org. Chem., 1989, 54, 3748-3749. See also reference 1. All new compounds gave satisfactory NMR data and either combustion analysis or HRMS data.
10. 4) Kursanov, D. N.; Parnes, Z. N.; Loim, N. M., Synthesis, 1974, 633-651.
11. 4 were confirmed by means of NOE enhancement experiments.
12. 6) Dougherty, D. A., Science, 1996, 271, 163-168 Kumpf R. A.; Dougherty, D. A., Science, 1993, 261, 17087-1710.
13. 6) Dougherty, D. A., Science, 1996, 271, 163-168 Kumpf R. A.; Dougherty, D. A., Science, 1993, 261, 17087-1710.
14. 7) Fleming, I., Frontier Orbitals and Organic Chemical Reactions, 1976, Wiley, New York. Fukui, K., Science, 1982, 218, 747-754.
15. 7) Fleming, I., Frontier Orbitals and Organic Chemical Reactions, 1976, Wiley, New York. Fukui, K., Science, 1982, 218, 747-754.
16. 13C NMR chemical shifts of the spiro carbon atoms of the diene (3b, 70.3 ppm; 3c, 71.2 ppm) were at lower fields than those of the corresponding olefins (2b, 63.3 ppm; 2d, 67.0 ppm; 2c, 63.8 ppm) and ketones (1b, 64.2 ppm; 1c, 64.9 ppm), or the corresponding cyclopentane derivatives (benzo[b]-, 57.2 ppm; benzo[c]-, 57.3 ppm). Semmelhack, M. F.; Foos, J. S.; Katz, S., J. Am. Chem. Soc., 1973, 95, 7325-7336. See also reference 2.
17. 9) Wilt, J, W.; Ahmed, S. Z., J. Org. Chem., 1979, 44, 4000-4002, Ishida, M.; Kakita, S.; Inagaki, S., Chem. Lett., 1995, 469-470.
18. 9) Wilt, J, W.; Ahmed, S. Z., J. Org. Chem., 1979, 44, 4000-4002, Ishida, M.; Kakita, S.; Inagaki, S., Chem. Lett., 1995, 469-470.
19. 10) In an attempt to increase the facial selectivity of the olefin derivatives, we prepared a dimethyl olefin analogue of 2b (re. 3), because the dimethyl substitution raises the occupied olefin π orbital, leading to a reduction of the relevant energy gap. However no significant facial selectivity (syn : anti =48 : 52) of the dimethyl analogue was observed in the epoxidation reaction, although enhanced reactivity (0.5 hr at -45°C), probably due to the raised olefin π orbital energy, was observed (ref. 5). This also indicates the effective orbital overlap of the diene systems due to the full spiro conjugation.
20. 11) Edman, J. R.; Simmons, H. E., J. Org. Chem., 1968, 33, 3808-3816. Mehta, G.; Padma, S.; Pattabhi, V.; Pramanik, A.; Chandrasekhar, J., J. Am. Chem. Soc., 1990, 112, 2942-2949.
21. 11) Edman, J. R.; Simmons, H. E., J. Org. Chem., 1968, 33, 3808-3816. Mehta, G.; Padma, S.; Pattabhi, V.; Pramanik, A.; Chandrasekhar, J., J. Am. Chem. Soc., 1990, 112, 2942-2949.
22. 12) Other possible orbital mechanisms are discussed in the following references. Halterman, R. L.; McEvoy, M. A., J. Am. Chem. Soc., 1992, 114, 980-985. Halterman, R. L.; McCarthy, B. A.; McEvoy, M. A., J. Org. Chem., 1992, 57, 5585-5589. Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, S., J. Am. Chem. Soc., 1990, 112, 8980-8982. Ishida, M.; Aoyama, T.; Beniya, Y.; Yarnabe, S.; Inagaki, S., Bull. Chem. Soc. Jpn., 1993, 66, 3430-3439. Frenking, G.; Köler, K. F.; Reetz, M. T., Angew. Chem. Int. Ed. Engl., 1991, 30, 1146-1149.
23. 12) Other possible orbital mechanisms are discussed in the following references. Halterman, R. L.; McEvoy, M. A., J. Am. Chem. Soc., 1992, 114, 980-985. Halterman, R. L.; McCarthy, B. A.; McEvoy, M. A., J. Org. Chem., 1992, 57, 5585-5589. Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, S., J. Am. Chem. Soc., 1990, 112, 8980-8982. Ishida, M.; Aoyama, T.; Beniya, Y.; Yarnabe, S.; Inagaki, S., Bull. Chem. Soc. Jpn., 1993, 66, 3430-3439. Frenking, G.; Köler, K. F.; Reetz, M. T., Angew. Chem. Int. Ed. Engl., 1991, 30, 1146-1149.
24. 12) Other possible orbital mechanisms are discussed in the following references. Halterman, R. L.; McEvoy, M. A., J. Am. Chem. Soc., 1992, 114, 980-985. Halterman, R. L.; McCarthy, B. A.; McEvoy, M. A., J. Org. Chem., 1992, 57, 5585-5589. Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, S., J. Am. Chem. Soc., 1990, 112, 8980-8982. Ishida, M.; Aoyama, T.; Beniya, Y.; Yarnabe, S.; Inagaki, S., Bull. Chem. Soc. Jpn., 1993, 66, 3430-3439. Frenking, G.; Köler, K. F.; Reetz, M. T., Angew. Chem. Int. Ed. Engl., 1991, 30, 1146-1149.
25. 12) Other possible orbital mechanisms are discussed in the following references. Halterman, R. L.; McEvoy, M. A., J. Am. Chem. Soc., 1992, 114, 980-985. Halterman, R. L.; McCarthy, B. A.; McEvoy, M. A., J. Org. Chem., 1992, 57, 5585-5589. Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, S., J. Am. Chem. Soc., 1990, 112, 8980-8982. Ishida, M.; Aoyama, T.; Beniya, Y.; Yarnabe, S.; Inagaki, S., Bull. Chem. Soc. Jpn., 1993, 66, 3430-3439. Frenking, G.; Köler, K. F.; Reetz, M. T., Angew. Chem. Int. Ed. Engl., 1991, 30, 1146-1149.
26. 12) Other possible orbital mechanisms are discussed in the following references. Halterman, R. L.; McEvoy, M. A., J. Am. Chem. Soc., 1992, 114, 980-985. Halterman, R. L.; McCarthy, B. A.; McEvoy, M. A., J. Org. Chem., 1992, 57, 5585-5589. Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, S., J. Am. Chem. Soc., 1990, 112, 8980-8982. Ishida, M.; Aoyama, T.; Beniya, Y.; Yarnabe, S.; Inagaki, S., Bull. Chem. Soc. Jpn., 1993, 66, 3430-3439. Frenking, G.; Köler, K. F.; Reetz, M. T., Angew. Chem. Int. Ed. Engl., 1991, 30, 1146-1149.
27. 13) These orbitals of the aromatic systems were selected according to the symmetry rule. In the case of ketone, the orbitals of the aromatic system were in an in-phase combination with a carbonyl π * orbital, and in the case of olefin or diene, the orbitals of the aromatic system were in an out-of-phase combination with an olefin or a diene π orbital. See reference 1.