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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
27
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pubmed:dateCreated |
2008-7-3
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pubmed:abstractText |
Lithium hexamethyldisilazide (LiHMDS) in triethylamine (Et 3N)/toluene is shown to enolize acyclic ketones and esters rapidly and with high E/ Z selectivity. Mechanistic studies reveal a dimer-based mechanism consistent with previous studies of LiHMDS/Et 3N. E/ Z equilibration occurs when <2.0 equiv of LiHMDS are used. Studies of the aldol condensation and Ireland-Claisen rearrangement of the resulting Et 3N-solvated enolates show higher and often complementary diastereoselectivities when compared with analogous reactions in THF. The Et 3N-solvated enolates also display a marked (20-fold) acceleration of the Ireland-Claisen rearrangement with evidence of autocatalysis. A possible importance of amine-solvated enolates is discussed.
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pubmed:grant |
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pubmed:commentsCorrections |
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11009360,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11348114,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11430056,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11456504,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11456518,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11457318,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11559177,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-11843594,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-12182578,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-12526460,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-12670196,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-14624589,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-14677981,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-15012141,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-15186185,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-15837788,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-15926847,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-15941273,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-16041407,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-16836294,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-16836298,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-16881665,
http://linkedlifedata.com/resource/pubmed/commentcorrection/18557616-17877405
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Jul
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pubmed:issn |
1520-5126
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pubmed:author |
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pubmed:issnType |
Electronic
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pubmed:day |
9
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pubmed:volume |
130
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
8726-32
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pubmed:dateRevised |
2011-7-20
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pubmed:meshHeading |
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pubmed:year |
2008
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pubmed:articleTitle |
Lithium hexamethyldisilazide-mediated enolizations: influence of triethylamine on E/Z selectivities and enolate reactivities.
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pubmed:affiliation |
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
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pubmed:publicationType |
Journal Article
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