The intramolecular Diels-Alder reactions of photochemically generated trans-cycloalkenones [10]

Journal of the American Chemical Society

Volumn 121, Issue 43, 1999, Pages 10229-10230

  Dorr, Hilary ^a   Rawal, Viresh H ^a  

^a UNIVERSITY OF CHICAGO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOALKANE DERIVATIVE; CYCLOHEXANE; GLASS; URANIUM;

CHEMICAL REACTION; CHEMICAL STRUCTURE; CONTROLLED STUDY; LETTER; LIGHT; PHOTOCHEMISTRY; STEREOISOMERISM; TEMPERATURE;

EID: 0033520754     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992287+     Document Type: Letter

References (22)

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20. In a typical procedure, a 0.015 M solution of the cycloheptenone 1 (0.50 mmol) in cyclohexane was degassed and irradiated through Pyrex at room temperature under an argon atmosphere. The solvent was removed and the product ketone isolated by flash column chromatography (15:1 hexane/ ethyl acetate). The diastereomers were separated by preparative HPLC.
21. 13C, HMQC, HMBC, COSY, and NOESY spectroscopy. The relative stereochemistry was determined by NOESY spectra, and some of the relevant NOE interactions are shown below (see Supporting Information). The structure assigned to 2′ should be considered tentative, since, while it is consistent with the NMR data, it is not incontrovertible. (Figure Presented)
22. The cis enone is considerably less reactive than the trans enone. In the absence of light, the thermal intramolecular Diels-Alder reaction of 1 did not take place even upon heating a xylene solution of 1 to 80°C for 2 h. Indeed, the cycloaddition proceeded only in refluxing xylenes (24 h), which afforded a 10:2:1 mixture of cycloadducts in 45% yield along with a small amount of recovered starting material and a considerable amount of decomposed (polymerized) material. The three cycloadducts of the above reaction were, as expected, structurally different from compounds 2, 2′, and 2″.