AI Article Synopsis
- The study explored the formation and rearrangement of oxonium ylides that included cyclopropylcarbinyl migrating groups.
- An efficient ring-contraction process through a [1,2]-shift resulted in the creation of cyclopropane-substituted cyclobutanones without any competing cyclopropane fragmentation.
- Using a specific mechanistic probe revealed cyclopropane fragmentation occurring via a heterolytic pathway, marking the first indication of ion pair intermediates from ylide cleavage and hinting at a new heterolytic mechanism for the Stevens [1,2]-shift.
Article Abstract
Formation and rearrangement of several oxonium ylides containing cyclopropylcarbinyl migrating groups were studied. Efficient ring-contraction by [1,2]-shift to form cyclopropane-substituted cyclobutanones was observed, with no competing cyclopropane fragmentation. Substitution with the hypersensitive mechanistic probe (trans,trans-2-methoxy-3-phenylcyclopropyl)methyl led to cyclopropane fragmentation via an apparent heterolytic pathway, providing the first evidence for ion pair intermediates from ylide cleavage, and suggesting a possible alternative heterolytic mechanism for the Stevens [1,2]-shift.
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| http://dx.doi.org/10.1039/c7cc07716e | DOI Listing |
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