Ring-Enlarging Cyclohexane Annulations

Journal of Organic Chemistry

Volumn 62, Issue 18, 1997, Pages 6379-6387

  Ando, Sumie ^a,b   Minor, Keith P ^a   Overman, Larry E ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b Asai Germanium Res Inst Co Ltd   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000767219     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970399i     Document Type: Article

References (41)

1. For brief reviews, see: (a) Overman, L. E. Aldrichimica Acta 1995, 28, 107. (b) Overman, L. E. Acc. Chem. Res. 1992, 25, 352. Overman, L. E. In Selectivities in Lewis Acid-Promoted Reactions; NATO ASSI Series 289; Schinzer, D., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; pp 1-20.
2. For brief reviews, see: (a) Overman, L. E. Aldrichimica Acta 1995, 28, 107. (b) Overman, L. E. Acc. Chem. Res. 1992, 25, 352. Overman, L. E. In Selectivities in Lewis Acid-Promoted Reactions; NATO ASSI Series 289; Schinzer, D., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; pp 1-20.
3. For brief reviews, see: (a) Overman, L. E. Aldrichimica Acta 1995, 28, 107. (b) Overman, L. E. Acc. Chem. Res. 1992, 25, 352. Overman, L. E. In Selectivities in Lewis Acid-Promoted Reactions; NATO ASSI Series 289; Schinzer, D., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; pp 1-20.
4. For our most recent application of this strategy in the construction of polycyclic ethers, see: MacMillan, D. W. C.; Overman, L. E. J. Am. Chem. Soc. 1995, 117, 10391.
5. Hirst, G. C.; Howard, P. N.; Overman, L. E. J. Am. Chem. Soc. 1989, 111, 1514.
6. For related ring-enlarging cyclopentene annulations, see: Johnson, T. O., Jr., Overman, L. E. Tetrahedron Lett. 1991, 32, 7361.
7. Hirst, G. C.; Johnson, T. O., Jr.; Overman, L. E. J. Am. Chem. Soc. 1993, 115, 2992.
8. (a) Stork, G.; Benaim, J. J. Am. Chem. Soc. 1971, 93, 5938.
9. (b) Battersby, A. R.; Buckley, D. G.; Staunton, J.; Williams, P. J. J. Chem. Soc., Perkin Trans. 1 1979, 2550.
10. Larchevêque, M.; Valette, G.; Cuvigny, T. Tetrahedron 1979, 35, 1745.
11. Imine 6 is prone to polymerization upon prolonged heating and was distilled in small batches.
12. (a) Maitte, P. Bull. Soc. Chim. Fr. 1959, 499.
13. (b) Ndebeka, G.; Raynal, S.; Caubére, P.; Bartsch, R. A. J. Org. Chem. 1980, 45, 5394.
14. 4), and concentrated. The crude styrenyl bromide was distilled under reduced pressure. The freshly distilled bromide (1.5-2.0 M) in THF was then added over 45 min to n-BuLi or s-BuLi (0.7 M) at -78°C. See also: Newman, M. S.; Dhawan, B.; Hashem, M. M; Khanna, V. K.; Springer, J. M. J. Org. Chem. 1976, 41, 3925.
15. Heathcock, C. H.; Jennings, R. A.; von Geldern, T. W. J. Org, Chem. 1983, 48, 3428.
16. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis; 2nd ed.; John Wiley: New York, 1991; Chapter 2.
17. 1H NMR signals at δ 4.2-4.5 for the acetal methine hydrogen) were typically components of this complex mixture.
18. (a) Avasthi, K.; Salomon, R. G. J. Org. Chem. 1988, 51, 2556.
19. (b) Battioni, J. P.; Capmau, M.-L.; Chodkiewicz, W. Bull. Soc. Chim. Fr. 1969, 976.
20. For a review, see: Ashby, E. C.; Laemmle, J. T. Chem. Rev. 1975, 75, 521.
21. (a) Condroski, K. R.; Ando, K.; Houk, K. N.; Wu, Y.-D.; Ly, S. K.; Overman, L. E., submitted for publication,
22. (b) Ly, S. K. Honors B.S. Thesis, University of California, Irvine, 1993.
23. Hoppe, D.; Lichtenberg, F. Angew. Chem., Int. Ed. Engl. 1984, 23, 239.
24. For the preparation of DTBMP and its use as a protic acid scavenger in Lewis acid-promoted reactions, see: (a) Anderson, A. G., Stang, P. J. Org. Synth. 1981, 60, 34 and references cited therein, (b) Hollis, T. K.; Bosnich, B. J. Am. Chem. Soc. 1995, 117, 4570. Cho, C. G.; Feit, B. A.; Webster, O. W. Macromolecules 1992, 25, 2081.
25. For the preparation of DTBMP and its use as a protic acid scavenger in Lewis acid-promoted reactions, see: (a) Anderson, A. G., Stang, P. J. Org. Synth. 1981, 60, 34 and references cited therein, (b) Hollis, T. K.; Bosnich, B. J. Am. Chem. Soc. 1995, 117, 4570. Cho, C. G.; Feit, B. A.; Webster, O. W. Macromolecules 1992, 25, 2081.
26. For the preparation of DTBMP and its use as a protic acid scavenger in Lewis acid-promoted reactions, see: (a) Anderson, A. G., Stang, P. J. Org. Synth. 1981, 60, 34 and references cited therein, (b) Hollis, T. K.; Bosnich, B. J. Am. Chem. Soc. 1995, 117, 4570. Cho, C. G.; Feit, B. A.; Webster, O. W. Macromolecules 1992, 25, 2081.
27. Ooi, T.; Maruoka, K.; Yamamoto, H. Org. Synth. 1993, 72, 95.
28. The authors have deposited atomic coordinates for this compound with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ. U.K.
29. Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
30. b. Equation presented.
31. The particular facility of 6-endo cationic cyclizations underpins the powerful polyene cyclization approaches to terpenes and steroids. For a recent review, see: Sutherland, J. K. In Comprehenive Organic Synthesis; Trost, B. M., Fleming, I., Ed.; Pergamon: Oxford, 1991; Vol. 3, p 341.
32. Mayr, H.; Patz, M. Angew. Chem., Int, Ed. Engl. 1994, 33, 938.
33. For example, the rate of carbocation formation is estimated to be 50 times faster from t-BuOH than from pinacol and 40 times faster from 2-butanol than from 1,2-propanediol: Herlihy, K. P. Aust. J. Chem. 1981, 34, 107.
34. Stereoelectronically favorable 1,2-shifts of carbocations can have very low activation barriers, see: Shubin, V. G. Top. Curr. Chem. 1984, 116/117, 261.
35. Minor, K. P.; Overman, L. E. Tetrahedron, 1997, 53, 8927.
36. Monte Carlo conformational searches were done using Macromodel version 5.5 and the MM2* forcefield, see: Chang, G.; Guida, W. C.; Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379. Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caulfield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. Saunders, M.; Houk, K. N.; Wu, Y.-D.; Still, W. C.; Lipton, M.; Chang, G.; Guida, W. C. J. Am. Chem. Soc. 1990, 112, 1419.
37. Monte Carlo conformational searches were done using Macromodel version 5.5 and the MM2* forcefield, see: Chang, G.; Guida, W. C.; Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379. Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caulfield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. Saunders, M.; Houk, K. N.; Wu, Y.-D.; Still, W. C.; Lipton, M.; Chang, G.; Guida, W. C. J. Am. Chem. Soc. 1990, 112, 1419.
38. Monte Carlo conformational searches were done using Macromodel version 5.5 and the MM2* forcefield, see: Chang, G.; Guida, W. C.; Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379. Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caulfield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. Saunders, M.; Houk, K. N.; Wu, Y.-D.; Still, W. C.; Lipton, M.; Chang, G.; Guida, W. C. J. Am. Chem. Soc. 1990, 112, 1419.
39. Alder, R. W.; East, S. P. Chem. Rev. 1996, 96, 2097.
40. 2 and toluene has been described; Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmera, F. J. Organometallics, 1996, 15, 1518.
41. 2. HPLC separations were performed using Waters Nova Silica, 6 μm, 19 mm × 300 mm, 8:1 hexane-EtOAc, 5 mL/min flow rate. Other general experimental details have been described: Deng, W.; Overman, L. E. J. Am. Chem. Soc. 1994, 116, 11241.