A stepwise retro-imino-ene as a key step in the mechanism of allene formation via the Crabbé acetylene homologation
Copyright © 2012 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 33(2012), 13 vom: 15. Mai, Seite 1236-9 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2012
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't Crabbé homologation Cu(I) catalysis KIE pericyclic reactions reaction mechanism Alkadienes propadiene 4AV0LZ8QKB mehr... |
| Zusammenfassung: | Copyright © 2012 Wiley Periodicals, Inc. The mechanism of the acetylene homologation procedure accidentally discovered and further developed by Crabbé and coworkers is unknown. Kinetic isotope effect (KIE) experiments, however, suggest that an intramolecular hydrogen shift is the key step of the transformation. In this work, we present a computational study of this mechanism. We found that the reaction proceeds via an unexpected stepwise retro-imino-ene rearrangement. This mechanism justifies the role of Cu(I) as a reaction catalyst and is also compatible with the KIE experiments reported |
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| Beschreibung: | Date Completed 30.06.2016 Date Revised 01.05.2015 published: Print-Electronic Citation Status MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.22954 |