CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS

HERTEL R, Mattay J, RUNSINK J (1991)
Journal of the American Chemical Society 113(2): 657-665.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The intramolecular cycloaddition reactions of the tetraene ethers 10 and 17 and the triene ether 28 were investigated. Acetone-sensitized excitation of 10 led to three intramolecular [2 + 2] cycloadducts 11-13. However, CuOTf-catalyzed photolysis of 10 gave two rearranged products 15 and 16 via copper(I)-catalyzed, photoinduced [1, 3] and [3, 3] rearrangement reactions of the divinylcyclobutane intermediates 11-13. The Cope product 14 is the precursor of the tetracyclic product 16 in a photocatalytic process. All photochemical products contain cis-fused rings. By analogy with the photochemical reactions of 10, acetone-sensitized photolysis of the tetraene ether 17 afforded four intramolecular [2 + 2] cycloadducts 18-21. The dipropenycyclobutanes 18-21 were formed as intermediates under CuOTf-catalyzed irradiation of 17 as well. However, longer irradiation times led to four rearranged products 22-25. Two cyclooctadiene intermediates 26 and 27 are the precursors of the tetracyclic products 24 and 25. Acetone-sensitized or CuOTf-catalyzed photolysis of the triene ether 28 gave two vinylcyclobutanes 29 and 30, but no copper(I)-catalyzed ring expansion reactions were found. Thermolysis of 10 in toluene at 150-degrees-C produced a mixture of four isomeric vinylcyclohexenes 31, 32, 15, and 33, whereas the CuOTf-catalyzed intramolecular Diels-Alder reaction in THF at 80-degrees-C showed an improved selectivity, the trans-fused hexahydroisobenzofuran derivative 31 being the main product. Thermolysis of 17 in toluene at 150-degrees-C gave two cyclohexene derivatives 22 and 34. Thermolysis of 28 at 150-degrees-C resulted in formation of two bicyclic cyclohexenes 35 and 36. Also, the thermal rearrangement reactions of the divinylcyclobutanes 11-13 and the dipropenylcyclobutanes 18-21 were studied. Initial experiments concerning the activity of copper(II) triflate as catalyst for the described intramolecular cycloaddition reactions were carried out.
Erscheinungsjahr
Zeitschriftentitel
Journal of the American Chemical Society
Band
113
Zeitschriftennummer
2
Seite
657-665
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HERTEL R, Mattay J, RUNSINK J. CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS. Journal of the American Chemical Society. 1991;113(2):657-665.
HERTEL, R., Mattay, J., & RUNSINK, J. (1991). CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS. Journal of the American Chemical Society, 113(2), 657-665. doi:10.1021/ja00002a039
HERTEL, R., Mattay, J., and RUNSINK, J. (1991). CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS. Journal of the American Chemical Society 113, 657-665.
HERTEL, R., Mattay, J., & RUNSINK, J., 1991. CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS. Journal of the American Chemical Society, 113(2), p 657-665.
R. HERTEL, J. Mattay, and J. RUNSINK, “CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS”, Journal of the American Chemical Society, vol. 113, 1991, pp. 657-665.
HERTEL, R., Mattay, J., RUNSINK, J.: CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS. Journal of the American Chemical Society. 113, 657-665 (1991).
HERTEL, R, Mattay, Jochen, and RUNSINK, J. “CYCLOADDITIONS .30. COPPER(I)-CATALYZED INTRAMOLECULAR DIENE-DIENE CYCLOADDITION REACTIONS AND REARRANGEMENTS”. Journal of the American Chemical Society 113.2 (1991): 657-665.