Photochemical rearrangement of 2,5-diphenyl-3 (2)-furanone

Padwa, Albert; Ku, Audrey; Sato, Eisuke F.

doi:10.1016/0040-4039(76)90005-8

Cited by 7 publications

(7 citation statements)

References 17 publications

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“…Initially, it was anticipated that ketone 3 might be obtained by the elimination of 2 equiv of HX from 5 which, in turn, might be prepared by the addition of X2 to the unknown ketone 6. In principle, 6 should be available by homologation of deltacyclan-8-one (7). Two related methods have been reported for the synthesis of 7.3,4 Recently, Watt and his co-workers have (1) For a review see: Tunemoto, D.; Hondo, K. Yuki Gosei Kagaku Kyokaishi 1977, 35, 1070-1086.…”

Section: Resultsmentioning

confidence: 99%

“…Treatment of 7 with tris(methylthio)methyllithium in tetrahydrofuran gave 12 in 75% yield. The stereochemistry assigned to the substituents in 12 follows from an examination of a molecular model of 7 which shows that attack at the endo face of the carbonyl carbon in 7 should be significantly impeded by the hydrogen at C-3. By contrast, there is no apparent steric hindrance to attack at the exo face of the carbonyl.…”

Section: Resultsmentioning

confidence: 99%

“…Deltacyclan-8-one (7). A solution of lithium diisopropylamide in tetrahydrofuran was prepared by the dropwise addition of n-butyllithium (2.83 mL of a 1.36 M solution in hexane, 3.85 mmol) to a stirred solution of diisopropylamine (394 mg, 3.90 mmol) in anhydrous tetrahydrofuran (6 mL) which was maintained at -78 °C under nitrogen.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of 4,5,9,10-tetradehydroadamantan-2-one

Israel¹,

Murray²

1985

J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis of 4,5,9,10-tetradehydroadamantan-2-one

Israel¹,

Murray²

1985

J. Org. Chem.

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“…The structure of 3 was confirmed by independent synthesis, and a pathway involving «-cleavage to 4, closure to 5, and then rearrangement to 3 was suggested to account for the observed reaction.7 Since these proposed steps have close analogies in the photochemistry of both cyclopentenones8 and 2-alkoxypyrrolin-5-ones,9 rearrangement of 2 to 3 appeared reasonable, and this result may well have discouraged further photochemical exploration in this series. We now report that none of the five alkyl-substituted 3(2ff)-furanones 6-10 behaves like 2 on irradiation; [6][7][8][9] undergo a novel isomerization, while 10 suffers two unexpected fragmentation reactions. Details are reported T h i s c o n t e n t i s below; photochemical results are given first, followed by preparative experiments.…”

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confidence: 99%

“…Photochemical Results. Irradiation of furanones [6][7][8][9] in benzene solution (~0.01 , > 280 nm) led in each case to a single isomeric compound as the only volatile product.…”

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confidence: 99%

Novel photochemical reactions of 3(2H)-furanones

Wolff¹,

Agosta²

1985

J. Org. Chem.

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6.O5,9]decan-3-one (24). A solution of potassium hydroxide (15.2 mg, 0.271 mmol) in methanol (1.5 mL) was added to a stirred solution of 23 (76.0 mg, 0.247 mmol) in methanol (5 mL), and the resulting solution was refluxed for 1 h. After cooling to room temperature, water (100 mL) was added and the reaction mixture was extracted with ether (3 X 25 mL). The combined ether extracts were washed with water (2 X 25 mL) and dried over anhydrous magnesium sulfate. Evaporation of the solvent at reduced pressure afforded a yellow oil which was Kugelrohr distilled to give 28.3 mg (50% yield) of 24. Analysis of this material by 13 3C NMR showed that 24 and 3 were present in a ratio of ca. 4:1. The 13C NMR resonances of 24 occur at 208.2 (C-3), 55.1 (d), 53.1 (t), 48.4 (d), 44.4 (d), 42.2 (d), 39.2 (d), 38.2 (t), 34.5 (d), 27.7 (d).4,5,9,10-Tetradehydroadamantan-2-one (3). A solution of potassium hydroxide (10.0 mg, 0.178 mmol) in methanol (1.0 mL) was added to a solution of a 4:1 mixture of 24 and 3, respectively, (27.0 mg, 0.119 mmol) in methanol (10 mL) and the resulting solution was refluxed for 1 h. After cooling, water (100 mL) was added and the reaction mixture was extracted with ether (3 X 25 mL). The combined ether extracts were washed with water (2 X 25 mL) and dried over anhydrous magnesium sulfate. Evaporation of the solvent at reduced pressure gave an oil which was column chromatographed on silica gel with methylene chloride-hexane-ether (45:45:10) as eluent to provide 7.2 mg of 3: mp 92-93 °C; NMR 2.60-2.52 (br s, 2 H), 2.46 (s, 2 H),

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