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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Abstract
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.
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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.
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.
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