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All compounds described in this work were prepared in racemic form
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All compounds described in this work were prepared in racemic form.
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All new compounds were identified by a combination of spectroscopic techniques, including 1D and 2D NMR spectroscopy. The relative stereochemistry was deduced from roesy or goesy experiments.
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All new compounds were identified by a combination of spectroscopic techniques, including 1D and 2D NMR spectroscopy. The relative stereochemistry was deduced from roesy or goesy experiments.
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Following the reviewers' suggestion, the reaction of vinyl allene 15 and 4-nitrobenzaldehyde was also studied. The electron-withdrawing group should inhibit the rearrangement because the cationic intermediate would not be stabilized by the phenyl group. The reaction yielded the expected cycloadducts in a 88% yield and 83:17 cis:trans ratio. Those compounds did not suffer the rearrangement under the conditions in which cis-19 and trans-19 were transformed into cis-22 and trans-22, providing additional support to the proposed mechanism (see Supporting Information for experimental details).
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Following the reviewers' suggestion, the reaction of vinyl allene 15 and 4-nitrobenzaldehyde was also studied. The electron-withdrawing group should inhibit the rearrangement because the cationic intermediate would not be stabilized by the phenyl group. The reaction yielded the expected cycloadducts in a 88% yield and 83:17 cis:trans ratio. Those compounds did not suffer the rearrangement under the conditions in which cis-19 and trans-19 were transformed into cis-22 and trans-22, providing additional support to the proposed mechanism (see Supporting Information for experimental details).
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