Kinetics and Stereochemistry of LiNR2-Induced 1,2-Elimination of Homoallylic Ethers

Journal of Organic Chemistry

Volumn 54, Issue 4, 1989, Pages 777-782

  Tobia, David ^a   Rickborn, Bruce ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542747456     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00265a013     Document Type: Article

References (21)

1. Portions of this work were presented at the 194th National Meeting of the American Chemical Society, New Orleans, Sept 2, 1987 (Orgn 160).
2. Svedberg, D. P. Ph.D. Dissertation, UCSB, 1979. Compound 1 was formed by LiAlH4 reduction of progesterone, followed by conversion to the bis methoxy ether; it contained ca. 65%,β isomer.
3. Crandall, J. K.; Arrington, J. P.; Hen, J. J. Am. Chem. Soc. 1967, 89, 6208. Marvell, E. N.; Rusay, R. J. Org. Chem. 1977, 42, 3336. Compound 6a was obtained in modest overall yield by a three-step procedure starting with cyclohexene and ethyl diazoacetate (carbenoid cyclopropane formation, reduction, and acid-catalyzed rearrangement). The cis alcohol 7a (ca. 95% isomeric purity) was obtained by Collins oxidation of 6a followed by L-Selectride reduction, with preparative GC used to obtain pure material. Carlson, R. G.; Huber, J. H.; Henton, D. E. J. Chem. Soc., Chem. Commun. 1973, 223. Lithium acetylide opening of cyclohexene oxide was followed by Na/NH3 reduction to form 6a. The authors noted that this procedure failed with cyclooctene oxide, as did efforts to open the latter epoxide with vinyllithium or lithium divinyl-copper.
4. Henin, F.; Muzart, J. Synth. Commun. 1984, 1355.
5. Wiberg, K. B.; Pfeiffer, J. G. J. Am. Chem. Soc. 1970, 92, 553. The trans alcohol 6a was also formed as a minor (26%) product from the treatment of cyclohexene oxide with vinylMgBr in THF.
6. Brockway, C.; Kocienski, P.; Pant, C. J. Chem. Soc., Perkin Trans. 1 1984, 875. The rate-enhancing effect suggested in this paper may also be invoked to explain the regioselectivity observed in, e.g., the work of Tius and Fauoq.8
7. Tius, M. A.; Fauq, A. H. J. Org. Chem. 1983, 48, 4131.
8. Others have commented on the difficulty of removing traces of Cu(II) salts, and these may be responsible for the inability to duplicate work between laboratories; see: Hutchinson, D. K.; Fuchs, P. L. J. Am. Chem. Soc. 1987, 109, 4930.
9. Chang, T. C. T.; Rosenblum, M.; Samuels, S. B. J. Am. Chem. Soc. 1980, 102, 5930. Hudrlik, P. F.; Kulkarni, A. K. J. Am. Chem. Soc. 1981, 103, 6251.
10. Hanack, M.; Schneider, H. J.; Schneider-Bernlohr, H. Tetrahedron 1967. 23. 2195.
11. Fleming, I.; Mah, T. J. Chem. Soc., Perkin Trans. 1 1975.,964.
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15. Letsinger, R. L.; Bobko, E. J. Am. Chem. Soc. 1953, 75, 2649. See also: Letsinger, R. L.; Pollart, D. F. J. Ore. Chem. 1956, 78, 6079.
16. Hunter, D. H.; Lin, Y. T. J. Am. Chem. Soc. 1968, 90, 5921. Hunter. D. H.: Sheering. D. J. J. Am. Chem. Soc. 1971. 93. 2348.
17. Thummel, R. P.; Rickborn, B. J. Am. Chem. Soc. 1970, 92, 2064; J. Org. Chem. 1972, 37, 3919.
18. de Koning, L. J.; Nibbering, N. M. M. J. Am. Chem. Soc. 1987, 109, 1715 and references therein.
19. Lappert, M. F.; Slade, M. J.; Singh, A.; Atwood, J. L.; Rogers, R. D.; Shakir, R. J. Am. Chem. Soc. 1983, 105, 302. Renaud, P.; Fox, M. A. J. Am. Chem. Soc. 1988, 110, 5702. Some time-dependent phenomena are discussed, which are similar to the slow aggregation of LTMP in ether proposed in the present study. Galiano-Roth, A. S.; Mi-chaelides, E. M.; Collum, D. B. J. Am. Chem. Soc. 1988, 110, 2658. Rogers, R. D.; Atwood, J. L.; Gruening, R. J. Organomet. Chem. 1978, 157, 229. Barr, D.; Clegg, W.; Mulvey, R. E.; Snaith, R. J. Chem. Soc., Chem. Commun. 1984, 285.
20. Moss, R. J.; Rickborn, B. J. Org. Chem. 1986, 51, 1992.
21. Grady, G. L.; Chokshi, S. K. Synthesis 1972, 483.