Activation of the ketone of 5-Cyclodecenones towards thermal transannular cyclization to give trans-hydroazulenols

Tetrahedron Letters

Volumn 38, Issue 41, 1997, Pages 7155-7158

  Fan, Weiming ^a   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

AZULENE DERIVATIVE;

ARTICLE; CYCLIZATION; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030657852     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01760-7     Document Type: Article

References (13)

1. Jisheng, L.; Gallardo, T.; White, J. B. J. Org. Chem. 1990, 55, 5426-5428.
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. Yongliang, C.; Hotchkin, D.; Tuazon, M.; White, J. B. Tetrahedron 1997, 53, in press.
6. Chu, Y.; Colclough, D.; White, J. B.; Smith, W. B. Magn. Reson. Chem. 1993, 31, 937-943.
7. 3SnLi (THF, 0 °C, 50-90%) gave the cis fused hydroazulenol 5.
8. Soderquist, J. A. Org. Syn. 1989, 68, 25-31.
9. 4, filtered, evaporated and purified by flash chromatography (30:1 hexane/EtOAc). Using this procedure, divinylcyclohexanol 9 was prepared reproducibly in gram quantities without contamination by α-hydroxyketone 10.
10. Only one alkene isomer was obtained in this experiment, but NOE experiments designed to determine the stereochemistry of the vinylsilane were ambiguous.
11. If the oxy-Cope rearrangement is carried out at room temperature with an excess of 18-crown-6, then [3,3]-sigmatropic rearrangement is accompanied by homo-Brook rearrangement, leading to desilylated cyclodecenones.
12. Demarco, P. V.; Farkas, E.; Doddrell, D.; Mylari, B. L.; Wenkert, E. J. Am. Chem. Soc. 1968, 90, 5480-5486.
13. 3): ∂ 152.4, 110.3, 85.8, 79.7, 65.4, 55.8, 38.2, 37.8, 31.9, 28.5, 24.8, 23.2, 15.6.