The Application Of Organo-hypervalent Iodine (â…¢) Reagent Iodosobenzene In The Intramolecular Aminofluorination Reaction And The Synthesis Of Vicinal Tricarbonyls

Organo-hypervalent iodine reagents are a class of easily prepared oxidants with the properties of stability towards atmospheric oxygen and moisture, low toxicity, high tunability in molecular design, and most importantly, excellent reactivity, and selectivity, which resulted in their broad application in the total synthesis of natural products, and new functional materials. It is worth noting that the past several years saw the great advance in the new reactivities of organo-hypervalent iodine reagents, and the design, synthesis, and reactivity of chiral organo-hypervalent iodine reagents.An iodosobenzene-mediated intramolecular aminofluorination reaction of homoallylic amines was developed to provide3-fluoropyrrolidines with a widely used Lewis acid boron trifluoride etherate (BF3-Et2O) acting as the fluorine source. A mechanism involving a carbocation intermediate was proposed on the basis of several experimental evidences.The vicinal tricarbonyl compounds are synthetic intermediates of proven value in organic synthesis. We developed a new protocol to efficiently prepare vicinal tricarbonyl compounds using PhIO with catalytic amount of Fe(NO3)3·9H2O under mild conditions. The method was applicable to many kinds of β-keto esters, β-diketones and β-keto amides substrates.