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The First α-Fluoroallenylphosphonate, the Synthesis of Conjugated Fluoroenynes, and the Stereoselective Synthesis of Vinylfluorophosphonates Using a New Multifunctional Fluorine-Containing Building Block
journal contribution
posted on 1999-12-17, 00:00 authored by Antonio J. Zapata, Yonghong Gu, Gerald B. HammondLimitations on current methodologies for the introduction of CF2 and CFH in complex α-fluorophosphonates led to the synthesis of a fluorine-containing building block TIPS-C⋮CCFXP(O)(OEt)2,
where X = H or F. This multifunctional fluorine synthon reacts with carbonyl compounds under
WHE conditions to give high yields of fluorinated conjugated enynes and enediyne. When X = F,
trapping of the desilylated anion with an electrophile after TIPS removal provided exclusive access
to γ-substituted derivatives of α-fluorophosphonates. When X = H, TBAF deprotection of the silyl
group yields H2CCCFP(O)(OEt)2 through an allenyl−propargyl resonance stabilized anion. The
allene moiety has been used as template in the stereoselective synthesis of α-fluoro-β,γ-diiodopropenyl phosphonate, via electrophilic iodination, and α-fluoro-γ-amino-α,β-unsaturated
phosphonates, including unsaturated phosphononucleosides, by nucleophilic displacement of an
allylic iodide. Hydroamination of H2CCCFP(O)(OEt)2 using secondary amines produced (Z)-α-fluoroenaminophosphonates, whereas Diels−Alder cycloaddition with cyclopentadiene provides the
corresponding exocyclic vinylfluorophosphonate.
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allenylderivativeConjugated FluoroenynesHydroaminationyieldallene moietyelectrophileallylic iodideStereoselective SynthesisNewphosphononucleosideaccesstemplateFirstTBAF deprotectionFluoroallenylphosphonateresonanceMultifunctionalTIPS removalexocyclic vinylfluorophosphonateVinylfluorophosphonateintroductionDielnucleophilic displacementenediyneLimitationaminesdesilylated anionWHE conditionsstereoselective synthesiscyclopentadienemethodologycycloadditionmultifunctional fluorine synthonCF 2carbonyl compoundselectrophilic iodinationCFH
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