Photochemical promotion of the intramolecular pauson - Khand Reaction. a new experimental protocol for cobalt-catalyzed [2 + 2 + 1] cycloadditions

Journal of the American Chemical Society

Volumn 118, Issue 9, 1996, Pages 2285-2286

  Pagenkopf, Brian L ^a   Livinghouse, Tom ^a  

^a MONTANA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO COMPOUND; CYCLOALKANE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; PHOTOCHEMISTRY; REACTION ANALYSIS;

EID: 0029871213     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9535975     Document Type: Article

References (28)

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9. 8, see:
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21. For recent applications of organometallic photochemistry in synthesis, see: (a) Rigby, J. H.; Ateeq, H. S.; Charles, N. R.; Cuisiat, S. V.; Ferguson, M. D.; Henshilwood, J. A.; Krueger, A. C.; Ogbu, C. O.; Short, K. M.; Heeg, M. J. J. Am. Chem. Soc. 1993, 115, 1382.
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23. Several instances of photochemically driven stoichiometric Pauson - Khand reactions which proceed in low vield have been reported: Brown, S. W.; Pauson, P. L. J. Chem. Soc., Perkin Trans. 1 1990, 1205.
24. 8 (Strem Chemical Co., Inc.) which was stored in a Vacuum Atmospheres drybox was utilized.
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26. Purchased at K-Mart. Inc., 1126 N. 7th Ave., Bozeman, MT.
27. 4), filtered, and concentrated in vacuo. The residual material was purified by chromatography on silica gel (30-50% EtOAc/hexane gradient for elution) to afford 127 mg (95%) of enone 1b as a slightly yellow oil. For preparative scale, longer irradiation times are required. Accordingly, a solution of enyne 1a (4.77 g, 20.0 mmol) and dicobalt octacarbonyl (214 mg, 0.8 mmol, 4 mol %) in degassed 1.2-DME (200 mL) was magnetically stirred at room temperature under an atmosphere of CO for 30 min. The resulting solution was then irradiated for 16 h at 50-55 °C. The reaction mixture was concentrated in vacuo, and the resulting oil was purified by chromatography on silica gel (10-50% EtOAc/hexane gradient for elution) to afford 4.41 g (83%) of enone 1b as a yellow oil.
28. Jung. M. E.; Gervay, J. J. Am. Chem. Soc. 1991, 113, 224.