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This selectivity for the cyclic alkene in limonene, as well as the lack of reactivity observed with 1-methylcyclopentene, cyclooctene, and in control experiments performed with other cyclic alkenes (α-pinene and 2-carene, for example) strongly suggest the intermediacy of highly strained (E)-cycloalkene intermediates. We also prefer this rationale over other possibilities, including reactivity arising from azole excited states being more acidic, for example
-
This selectivity for the cyclic alkene in limonene, as well as the lack of reactivity observed with 1-methylcyclopentene, cyclooctene, and in control experiments performed with other cyclic alkenes (α-pinene and 2-carene, for example) strongly suggest the intermediacy of highly strained (E)-cycloalkene intermediates. We also prefer this rationale over other possibilities, including reactivity arising from azole excited states being more acidic, for example.
-
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44
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38849178495
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In agreement with this rationale, the limonene recovered from the reaction shown in eq 8 was found to be racemic. See the experimental details
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In agreement with this rationale, the limonene recovered from the reaction shown in eq 8 was found to be racemic. See the experimental details.
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45
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See ref 12 for a discussion. For an example of application in total synthesis, see: Marshall, J. A.; Pike, M. T. J. Org. Chem. 1968, 33, 435.
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