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note
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2 protons at the C-2′ position. The detailed analysis will be reported elsewhere.
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Upon being left to stand at room temperature, the hydroperoxide converts into the corresponding alcohol with a constant stereoisomeric ratio and without formation of any by-products by the ferric porphyrin catalyst 1. This highly selective transformation of hydroperoxide/alcohol was confirmed by the separate reaction of the isolated hydroperoxide with 1. The detailed mechanism will be discussed elsewhere.
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23
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0038759120
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note
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The reaction of the diene 3 with oxoiron(IV) porphyrin π cation radical 2′ at-35°C also gave a trace amount (<5%) of the corresponding monoepoxide without any of the accompanying dienyl alcohols.
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2 in toluene according to the reported method; A. L. Balch, J. Am. Chem. Soc. 1984, 106, 7779-7785. Addition of the diene 3 to this ferryl porphyrin solution at-35°C resulted in the complete recovery of the diene. It is generally accepted that a ferryl complex-does not catalyze H-abstraction or oxygen-atom transfer.
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Ordinary autoxidation of the diene in air gives the same hydroperoxide without any stereoselectivity (5-trans-7-cis:5-trans-7-trans = 1:1).
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