%0 Journal Article
%A Zapata, Antonio J.
%A Gu, Yonghong
%A Hammond, Gerald B.
%D 1999
%T The First α-Fluoroallenylphosphonate, the Synthesis of
Conjugated Fluoroenynes, and the Stereoselective Synthesis of
Vinylfluorophosphonates Using a New Multifunctional
Fluorine-Containing Building Block
%U https://acs.figshare.com/articles/journal_contribution/The_First_-Fluoroallenylphosphonate_the_Synthesis_of_Conjugated_Fluoroenynes_and_the_Stereoselective_Synthesis_of_Vinylfluorophosphonates_Using_a_New_Multifunctional_Fluorine-Containing_Building_Block/3720297
%R 10.1021/jo991620p.s001
%2 https://acs.figshare.com/ndownloader/files/5811993
%K allenyl
%K derivative
%K Conjugated Fluoroenynes
%K Hydroamination
%K yield
%K allene moiety
%K electrophile
%K allylic iodide
%K Stereoselective Synthesis
%K New
%K phosphononucleoside
%K access
%K template
%K First
%K TBAF deprotection
%K Fluoroallenylphosphonate
%K resonance
%K Multifunctional
%K TIPS removal
%K exocyclic vinylfluorophosphonate
%K Vinylfluorophosphonate
%K introduction
%K Diel
%K nucleophilic displacement
%K enediyne
%K Limitation
%K amines
%K desilylated anion
%K WHE conditions
%K stereoselective synthesis
%K cyclopentadiene
%K methodology
%K cycloaddition
%K multifunctional fluorine synthon
%K CF 2
%K carbonyl compounds
%K electrophilic iodination
%K CFH
%X Limitations 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.
%I ACS Publications