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The Diels-Alder reaction of 5, or alkyl analogues, with much less hindered dienes has been reported: (a) Forte, M.; Orsini, F.; Pelizzoni, F.; Ricca, G. Gazz. Chim. Ital. 1985, 115, 41.
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The Diels-Alder reaction of 5, or alkyl analogues, with much less hindered dienes has been reported: (a) Forte, M.; Orsini, F.; Pelizzoni, F.; Ricca, G. Gazz. Chim. Ital. 1985, 115, 41.
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Such [4 + 2] cycloadditions are known, as are the simple dimerization of o-benzoquinones. (a) Al-Talib, M.; Gerstenberger, I.; Jones, P. G.; Winterfeldt, E. Liebigs Ann./Recl. 1997, 893.
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Such [4 + 2] cycloadditions are known, as are the simple dimerization of o-benzoquinones. (a) Al-Talib, M.; Gerstenberger, I.; Jones, P. G.; Winterfeldt, E. Liebigs Ann./Recl. 1997, 893.
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For a different mode of 1,4-addition, see
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For a different mode of 1,4-addition, see: Nair, V.; Rajesh, C.; Dhanya, R.; Rath, N. P. Tetrahedron Lett. 2002, 43, 5349.
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These compounds were quite difficult to separate and purify by normal silica gel chromatography because of their tendency to adhere to the column, which made elution difficult at times
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These compounds were quite difficult to separate and purify by normal silica gel chromatography because of their tendency to adhere to the column, which made elution difficult at times.
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84868939042
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General Procedure for the Oxidation-Cyclization. To a solution of methyl 3,4-dihydroxybenzoate 8 (1.0 mmol) and the silyl enol ether 13 (4 mmol) in 8 mL of THF at 0 °C was added 2 mL (1.1 mmol) of bis(trifluoroacetoxy) iodobenzene (0.55 M solution in THF) dropwise over 10 min, forming a green solution initially. The reaction was allowed to stir at 0 °C (unless specified otherwise) for 4 h, the solution becoming a dark yellow. To the solution was added 0.5 mL of HC1 (4 M solution in dioxane) and 1.0 mL of methanol. The mixture was refluxed for 1 h, and the solution lightened in color. The solution was extracted with 30 mL of diethyl ether, washed with 2 × 10 mL saturated NaHCO3 and 1 × 10 mL brine, dried over MgSO4, filtered, and concentrated in vacuo to yield an oily residue. The residue was purified by flash column chromatography over silica gel (ether and hexanes) to yield the benzofuran product 14. The products were ofte
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4, filtered, and concentrated in vacuo to yield an oily residue. The residue was purified by flash column chromatography over silica gel (ether and hexanes) to yield the benzofuran product 14. The products were often recrystallized to give purer material.
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