Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones
Garam Choi, Ha Eun Kim, Sunjoo Hwang, Han-Na Jang, Won‐jin Chung
Abstract
Tetrasubstituted carbon containing two different halogen substituents was constructed in a single-step operation by utilizing the carbene-like reactivity of dioxaphospholene through the tandem reaction of electrophilic and nucleophilic halogenating reagents. It was crucial to devise non-dealkylatable phosphoramidite, which enabled the efficient formation of geminal chlorofluorides from various 1,2-diketones with (PhSO2)2NF and n-Bu4NCl. In addition, selective functionalization of the chlorine substituent was demonstrated, and the absence of halogen scrambling was confirmed.
Topics & Concepts
GeminalChemistryNucleophileHalogenUmpolungReactivity (psychology)SubstituentElectrophilePhosphoramiditeCombinatorial chemistryReagentPhosphorusCarbeneTandemChlorineMedicinal chemistryOrganic chemistryCatalysisAlkylMaterials scienceBiochemistryDNAAlternative medicineComposite materialMedicinePathologyOligonucleotideFluorine in Organic ChemistrySynthesis and Catalytic ReactionsSynthesis and Reactions of Organic Compounds