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231224s2012 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.22954
|2 doi
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|a pubmed24n0719.xml
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|a DE-627
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|a eng
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|a González, Marta
|e verfasserin
|4 aut
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|a A stepwise retro-imino-ene as a key step in the mechanism of allene formation via the Crabbé acetylene homologation
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|c 2012
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|a Date Completed 30.06.2016
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|a Date Revised 01.05.2015
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a Copyright © 2012 Wiley Periodicals, Inc.
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|a 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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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a Crabbé homologation
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|a Cu(I) catalysis
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|a KIE
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|a pericyclic reactions
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|a reaction mechanism
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|a Alkadienes
|2 NLM
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|a propadiene
|2 NLM
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|a 4AV0LZ8QKB
|2 NLM
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|a Copper
|2 NLM
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|a 789U1901C5
|2 NLM
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|a Acetylene
|2 NLM
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|a OC7TV75O83
|2 NLM
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|a Rodríguez, Roi Álvarez
|e verfasserin
|4 aut
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|a Cid, Maria Magdalena
|e verfasserin
|4 aut
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|a López, Carlos Silva
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 33(2012), 13 vom: 15. Mai, Seite 1236-9
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:33
|g year:2012
|g number:13
|g day:15
|g month:05
|g pages:1236-9
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|u http://dx.doi.org/10.1002/jcc.22954
|3 Volltext
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