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For selected examples on sequences proceeding by π activation with concomitant nucleophilic trapping, see, for example: Alkynes: a P. Y. Toullec, E. Genin, L. Leseurre, J.-P. Genêt, V. Michelet, Angew. Chem. 2006, 118, 7587;
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Addition of tBuOH (1.1 equiv) provided 2a in 86% yield, while the use of MeOH produced a mixture of unidentified compounds.
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Addition of tBuOH (1.1 equiv) provided 2a in 86% yield, while the use of MeOH produced a mixture of unidentified compounds.
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65
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34250880490
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The rearrangement of 1,5-enyne precursors was strictly limited to substrates that contain alkenes bearing an additional substituent at C2. Attempted rearrangement of 1,2-disubstituted alkenes afforded at most trace amounts of the desired cyclopentene under the reaction conditions. In these cases, the formation of the major product can be rationalized by a sequence consisting of elimination and subsequent hydration of the triple bond.
-
The rearrangement of 1,5-enyne precursors was strictly limited to substrates that contain alkenes bearing an additional substituent at C2. Attempted rearrangement of 1,2-disubstituted alkenes afforded at most trace amounts of the desired cyclopentene under the reaction conditions. In these cases, the formation of the major product can be rationalized by a sequence consisting of elimination and subsequent hydration of the triple bond.
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66
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1H NMR analysis of crude reaction mixtures.
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1H NMR analysis of crude reaction mixtures.
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