Prins-pinacol spiroannulations

Tetrahedron

Volumn 53, Issue 26, 1997, Pages 8927-8940

  Minor, Keith P ^a   Overman, Larry E ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PINACOL; SPIRO[4,5]DECANONE 22; SPIRO[4,5]DECANONE 25; SPIRO[4,5]DECANONE 29; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; DRUG CONFORMATION; DRUG SYNTHESIS; DRUG TRANSFORMATION; NUCLEAR MAGNETIC RESONANCE; PREDICTION; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0030877492     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(97)90401-4     Document Type: Article

References (38)

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 for the construction of polycyclic ethers, see: MacMillan, D. W. C.; Overman, L. E. J. Am. Chem. Soc. 1995, 117, 10391.
5. (a) Hirst, G. C.; Howard, P. N.; Overman, L. E. J. Am. Chem. Soc. 1989, 111, 1514.
6. (b) For a related ring-enlarging cyclopentene annulation, see: Johnson, T. O., Jr.; Overman, L. E. Tetrahedron Lett. 1991, 52, 7361.
7. Hirst, G. C.; Johnson, T. O., Jr.; Overman, L. E. J. Am. Chem. Soc. 1993, 115, 2992.
8. (a) Paquette, L. A.; Lin, H.-S.; Gallucci, J. C. Tetrahedron Lett. 1987, 28, 1363.
9. (b) Rubottom, G. M.; Gruber, J. M.; Boeckman, R. K., Jr.; Ramaiah, M.; Medwid, J. B. Tetrahedron Lett. 1978, 4603.
10. Kaupp, G.; Frey, H.; Behmann, G. Chem. Ber. 1988, 121, 2127.
11. Molecular mechanics calculations indicate that 15 and 16, as expected, strongly prefer chair cyclohexane conformations having the t-butyl group equatorial.
12. Omura, K.; Swern, D. Tetrahedron 1978, 34, 1651.
13. Montgomery, J.; Overman, L. E. J. Org. Chem. 1993, 58, 6476.
14. TMSOTf was distilled from poly(4-vinylpyridine) prior to use.
15. 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.
16. 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.
17. Carlsen, H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
18. 1 is reported for 2,2-dimethylcyclohexane-1,4-dione, see: Yamamoto, Y.; Oritani, T.; Koga, H.; Horiuchi, T.; Yamashita, K. Agric. Biol. Chem. 1990, 54, 1915.
19. The authors have deposited atomic coordinates for 26 and 30 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, UK.
20. (a) Trost, B. M.; Murayama, E. J. Am. Chem. Soc. 1981, 103, 6529.
21. (b) Preparation: Meerwein, H.; Zenner, K.-F.; Gipp, R. Liebigs Ann. Chem. 1965, 688, 67.
22. (a) Pauling electronegativities of C and S are identical. (b) An inductive explanation is also ruled out if the pinacol rearrangement has an early transition state, since electron-withdrawal by the methoxy substituent would lower the migratory aptitude of bond a.
23. relMM2* 0 1.4 (kcal/mol) dihedral angle 43° 61°
24. Monte Carlo conformational searches were done using Macromodel version 5.5, see: Chang, G.; Guida, W. C., Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379.
25. Stereoelectronically favorable 1,2-shifts of carbocations can have very low activation barriers, see: Shubin, V. G. Topics in Current Chemistry 1984, 116/117, 267.
26. We suggest that 16 cyclizes in a similar sense by way of a twist-boat conformation.
27. For investigations of the generation of 9-decalyl cations by solvolysis, see: (a) Fort, R. C., Jr.; Hornish, R. E.; Liang, G. A. J. Am. Chem. Soc. 1970, 92, 7558. (b) Gream, G. E. Aust. J. Chem. 1972, 25, 1051. Becker, K. B.; Boschung, A., F.; Geisel, M.; Grob, C. A. Helv. Chem. Acta 1973, 56, 2747.
28. For investigations of the generation of 9-decalyl cations by solvolysis, see: (a) Fort, R. C., Jr.; Hornish, R. E.; Liang, G. A. J. Am. Chem. Soc. 1970, 92, 7558. (b) Gream, G. E. Aust. J. Chem. 1972, 25, 1051. Becker, K. B.; Boschung, A., F.; Geisel, M.; Grob, C. A. Helv. Chem. Acta 1973, 56, 2747.
29. For investigations of the generation of 9-decalyl cations by solvolysis, see: (a) Fort, R. C., Jr.; Hornish, R. E.; Liang, G. A. J. Am. Chem. Soc. 1970, 92, 7558. (b) Gream, G. E. Aust. J. Chem. 1972, 25, 1051. Becker, K. B.; Boschung, A., F.; Geisel, M.; Grob, C. A. Helv. Chem. Acta 1973, 56, 2747.
30. 2. Other general experimental details have been detailed: Deng, W.; Overman, L. E. J. Am. Chem. Soc. 1994, 116, 11241.
31. 2. Other general experimental details have been detailed: Deng, W.; Overman, L. E. J. Am. Chem. Soc. 1994, 116, 11241.
32. Larchevêque, M.; Valette, G.; Cuvigny, T. Tetrahedron 1979, 35, 1745.
33. Stork, G.; Benaim, J. J. Am. Chem. Soc. 1971, 93, 5938.
34. Battersby, A. R.; Buckley, D. G.; Staunton, J.; Williams, P. J. J. Chem. Soc. Perkin Trans. I 1979, 10, 2550.
35. Perrin D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals; Pergamon Press: New York, 1988; p 123.
36. 3N is an efficient way to prepare siloxy ketone 17 (69% after distillation). For other procedures see: (a) ref 5b. (b) Wilson, S. R.; Walters, M. E.; Orbaugh, B. J. Org. Chem. 1976, 41, 378. Creary, X.; Rollin, A. J. J. Org. Chem. 1979, 44, 1017.
37. 3N is an efficient way to prepare siloxy ketone 17 (69% after distillation). For other procedures see: (a) ref 5b. (b) Wilson, S. R.; Walters, M. E.; Orbaugh, B. J. Org. Chem. 1976, 41, 378. Creary, X.; Rollin, A. J. J. Org. Chem. 1979, 44, 1017.
38. 3N is an efficient way to prepare siloxy ketone 17 (69% after distillation). For other procedures see: (a) ref 5b. (b) Wilson, S. R.; Walters, M. E.; Orbaugh, B. J. Org. Chem. 1976, 41, 378. Creary, X.; Rollin, A. J. J. Org. Chem. 1979, 44, 1017.