Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 35, Pages 12182-12189Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b05057
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- National Institutes of Health [GM077167, GM039764]
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Etiolizations Of highly substituted acyclic ketones used-in the syntheses of tetrasubstituted olefin-based anticancer agents are described. Lithium hexamethyldisilazide (LiHMDS)-mediated enolizations are moderately Z-selective in neat tetrahydrofuran (THF) and E-selective in 2.0 M THF-/hexane. The results of NMR spectroscopy show the resulting enolates to be statistically distributed ensembles of E,E-, E,Z-, and Z,Z-enolate dimers with subunits that reflect the selectivities. The results of rate studies trace the preference for E and Z iomers to tetrasolvated- and pentasolvated-monomer-based transition structures; respectively. Enolization using LiHMDS in N,N-dimethylethylamine or triethylamine in toluene affords a 65:1 mixture of enolate mixed dimers containing E and Z isomers, respectively. Spectroscopic studies show that condition, dependent complexation of ketone to LiHMDS occurs in trialkylamine/toluene. Rate data attribute the high selectivity exclusively to monosolvated-dimer-based transition structures.
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