%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 H2CCCFP(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 H2CCCFP(O)(OEt)2 using secondary amines produced (Z)-α-fluoroenaminophosphonates, whereas Diels−Alder cycloaddition with cyclopentadiene provides the corresponding exocyclic vinylfluorophosphonate. %I ACS Publications