Synthesis of a cis-5-cyclodecedone and cis fused hydronaphthalenols through control of the stereochemistry of the oxy-cope rearrangement with the tri-n-propylsilyl substituent

Tetrahedron

Volumn 53, Issue 42, 1997, Pages 14235-14246

  Chu, Yongliang ^a   Colclough, David ^a   Hotchkin, David ^b   Tuazon, Myla ^b   White, James B ^b  

^a UNIVERSITY OF TEXAS AT ARLINGTON   (United States)

^b PEPPERDINE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOALKANE DERIVATIVE; NAPHTHALENE DERIVATIVE;

ARTICLE; CHIRALITY; CYCLIZATION; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

OXY;

EID: 0030845836     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(97)00952-6     Document Type: Article

References (22)

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2. Fan, W.; White, J. B. Tetrahedron Lett. 1993, 34, 957-960.
3. Fan, W.; White, J. B. J. Org. Chem. 1993, 58, 3557-3562.
4. Colclough, D.; White, J. B.; Smith, W. B. and Chu, Y. J. Org. Chem. 1993, 58, 6303-6313.
5. 2, RT, two days) led to recovered starting material along with cis-5-cyclodecenone and the product from transannular cyclization of cis-5-cyclodecenone, indicating that protodesilylation is faster than cyclization for vinylsilane 26. (formula presented)
6. Nishino, M; Kondo, H ; Miyake, A. Chem. Lett. 1973, 667-670.
7. Kato, T.; Kondo, H.; Nishino, M.; Tanaka, M.; Hata, G.; Miyake, A. Bull. Chem. Soc. Jpn. 1980, 53, 2958-2961.
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12. Spinazzé, P. G., Keay, B. A. Tetrahedron Lett. 1989, 30, 1765-1768 and references therein.
13. Urabe, H. ; Kuwajima, I. Tetrahedron Lett. 1983, 24, 4241-4244.
14. 3 of cis- and trans-5-cyclodecenones. The δ of the carbonyl carbon of cis isomers is downfield of the δ of the trans isomers (214.4-215.1 ppm versus 212.5-213.0 ppm). In addition, the cis isomers have chemical shifts at 34.6 ± 0.2 and 23.4 ± 0.2 ppm that are absent in the spectra of the trans isomers. These trends have been observed for the unsubstituted and for 5-, 6-, and 7-substituted 5-cyclodecenones.
15. We thank Professor Martin Pomerantz, Department of Chemistry and Biochemistry, The University of Texas at Arlington, for suggesting to us concurrent hydride migration with cyclization.
16. Siegel, S.; Smith, G. V. J. Am. Chem. Soc. 1960, 82, 6082-6087.
17. Molander, G. A.; Etter, J. B. J. Org. Chem. 1986, 51, 1778-1786.
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19. For examples of cis-1,2-divinylcyclohexanols undergoing anionic oxy-Cope rearrangement to give cis-5-cyclodecenones, see references 1, 20 and 21. Rearrangement of cis-1,2-divinylcyclohexanols can take place from either of two conformations: one in which the oxyanion is equatorial with respect to the cyclohexane ring, which leads to a cis-5-cyclodecenone, and one in which the oxyanion is axial, which leads to the trans-5-cyclodecenone. If there are no additional substituents on the cyclohexane ring, as is the case for the examples found in references 1 and 20, then anionic oxy-Cope rearrangement is observed to take place with the oxyanion in the equatorial position, which minimizes the number of axial substituents in the transition state, leading to the cis-5-cyclodecenone. In the one example of an anionic oxy-Cope rearrangement of a cis-1,2-divinylcyclohexanol with four substituents on the cyclohexane ring (reference 21), there are two substituents axial and two substituents equatorial regardless of whether the oxyanion is axial or equatorial; in this example the cw-1,2-divinylcyclohexanol rearranged predominantly through the pathway in which the oxyanion was axial, leading to a 97:3 ratio of the trans- and cis-5-cyclodecenones.
20. Sworin, M; Lin, K.-C. J. Am. Chem. Soc. 1989, 111, 1815-1825.
21. Clive, D. L. J.; Russell, C. G.; Suri, S. C. J. Org. Chem. 1982, 47, 1632-1641.
22. Winkle, M. R.; Lansinger, J. M.; Ronald, R. C. J. Chem. Soc., Chem. Commun. 1980, 87-88.