Preparation Of Polystyrene-supported Propargly Sulfone And Its Application In Solid-phase Orgnic Synthesis Of Heterocyclic Compounds

In this paper, the application of polystyrene-supported sulfonyl compounds andthe recent progress on the study of isoxazoles and1,2,3-triazoles were investigatedfirstly. Following, we mainly explore the preparation of polystyrene-supportedpropargyl sulfone reagent and its application in solid-phase organic synthesis of3,5-disubstituted isoxazole and1,2,3-triazole compounds. The main content of thispaper were as follows:Primary, Starting with polystyrene(styrene/1%divinylbenzene-styrenecopolymer)-supported sodium benzenesulfinate, reacted with2,3-dibromoprop-1-eneto afforded polystyrene-supported2-bromopropene sulfone, which was further treatedwith tetrabutylammonium fluoride (TBAF) to eliminate the HBr and the targetpolystyrene-supported propargyl sulfone reagent was obtained. Thenpolystyrene-supported propargyl sulfone was reacted with different aryl aldoximethrough the1,3-dipolar cycloaddition reaction to afforded polystyrene-supported3,5-disubstituted-isoxazoles. Finally, under a mild room temperature condition,treated the intermedium resin with Mg/HgCl2in a mixed solvent (DMF/CH3OH),cleavage the resin and obtained the target product of3-substituted-5-methylisoxazolecompounds. The advantages of this method was easy to operate in a mild condition,and with good yield (60-89%) and high purity (94-98%).Based on the above, under the condition of low temperature (-78oC), treatmentof polystyrene-supported3,5-disubstituted-isoxazoles resin with Lithiumdiisopropylamide (LDA), then alkylating with primary halogenoalkanearyl(RCH2Br),the target products of3-substitued-5-[(E)-2-sustutited-vinyl]isoxazole compoundswere obtained followed by cleavage the resin with triethylamine at room temperature.The advantages of this method was easy to operate in a mild condition with goodyield (75-85%) and high purity (93-95%). Thirdly, Starting with polystyrene-supported propargyl sulfone reagent, reactedwith organic azide compounds through the [3+2] cycloaddition reaction under theexist of base and catalyst to afforded polystyrene-supported1,4-disubstitued-1,2,3-triazole. which was further treated with LDA under theconditions of low temperature (-78oC), and then alkylating with CH3I. Finally, the1-substitued-4-vinyl-1,2,3-triazoles were obtained after cleavage the intermediumresin with triethylamine at a mild condition of zero to room temperature. Theadvantages of this method was easy to operate in a mild condition, and with goodyield (68-93%) and also with high purity (93-96%).