Rapid Synthesis of Di- and Triquinanes by Direct Reductive Fragmentation of Paterno - Büchi-Derived Oxetanes

Journal of Organic Chemistry

Volumn 63, Issue 16, 1998, Pages 5302-5303

  Dvorak, Curt A ^b   Dufour, Claire ^b   Iwasa, Seiji ^b   Rawal, Viresh H ^a  

^a UNIVERSITY OF CHICAGO   (United States)

^b NONE

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0012647320     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980814m     Document Type: Article

References (23)

1. An ideal synthesis, as defined by Professor Paul A. Wender (Starford), is one that leads to the target molecule in "one step and 100% yield from readily available materials." See: Chem. Eng. News 1997, May 5, p 47. See also: Wender, P. A.; Handy, S.; Wright, D. L. Chem. Ind. (London) 1997, 765-769.
2. An ideal synthesis, as defined by Professor Paul A. Wender (Starford), is one that leads to the target molecule in "one step and 100% yield from readily available materials." See: Chem. Eng. News 1997, May 5, p 47. See also: Wender, P. A.; Handy, S.; Wright, D. L. Chem. Ind. (London) 1997, 765-769.
3. Review of quinane syntheses: Mehta, G.; Srikrishna, A. Chem. Rev. 1997, 97, 671-719.
4. Rawal, V. H.; Dufour, C. J. Am. Chem. Soc. 1994, 116, 2613-2614.
5. (a) Rawal, V. H.; Dufour, C.; Eschbach, A. J. Chem. Soc., Chem. Commun. 1994, 1797-1798.
6. (b) Rawal, V. H.; Dufour, C.; Iwasa, S. Tetrahedron Lett. 1995, 36, 19-22.
7. (c) Rawal, V. H.; Fabré, A.; Iwasa, S. Tetrahedron Lett. 1995, 36, 6851-6854.
8. (d) Rawal, V. H.; Eschbach, A.; Dufour, C.; Iwasa, S. Pure Appl. Chem. 1996, 68, 675-678.
9. (e) Dufour, C.; Iwasa, S.; Fabré, A.; Rawal, V. H. Tetrahedron Lett. 1996, 37, 7867-7870.
10. (f) Dvorak, C. A.; Rawal, V. H. J. Chem. Soc., Chem. Commun. 1997, 2381-2382.
11. Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161.
12. (a) Cohen, T.; Jeong, I. H.; Mudryk, B.; Bhupathy, M.; Awad, M. J. Org. Chem. 1990, 55, 1528-1536.
13. (b) Mudryk, B.; Cohen, T. J. Org. Chem. 1991, 56, 5760-5761.
14. (c) Mudryk, B.; Cohen, T. J. Am. Chem. Soc. 1991, 113, 1866-1867.
15. 4 in ether gives predominantly the epimeric allylic alcohol (13:1, α-OH/β-OH). The spectral properties of the minor component of the reduction corresponded perfectly with alchohol 5.
16. Oxidation of the allylic alcohol using PDC in DMF afforded in 90% yield the corresponding enone, the key diquinane precursor in our isocomene syntnesis. This two-step conversion of oxetane 10 to the enone effectively shortnes our isocomene synthesis by one step and significantly improves the overall yield of the synthesis to ∼40%, rivaling that of Pirrung's synthesis of isocomene (34% overall yield from 1,3-cyclohexanedione; see ref 10).
17. Pirrung, M. C. J. Am. Chem. Soc. 1981, 103, 82-87.
18. The ratio was determined by GC and was consistent with the isolated ratio of the two pure compounds, obtained by MPLC separation of the mixture.
19. The structural assignment was based on decoupling and NOE experiments carried out on 300 and 500 MHz NMR instruments.
20. Sauers, R. R.; Henderson, T. R. J. Org. Chem. 1974, 39, 1850-1853. See also: VanderDoes, T.; Klumpp, G. W.; Schakel, M. Tetrahedron Lett. 1986, 27, 519-520.
21. Sauers, R. R.; Henderson, T. R. J. Org. Chem. 1974, 39, 1850-1853. See also: VanderDoes, T.; Klumpp, G. W.; Schakel, M. Tetrahedron Lett. 1986, 27, 519-520.
22. Dvorak, C. A. Ph.D. Thesis, The University of Chicago, 1998.
23. Attempts to carry out the reactions in a different solvent system (diethyl ether, tert-butylmethyl ether, hexane, DME, or combinations thereof) have so far proved unsuccessful as LDBB formation could not be induced.