Study On Functionalization Of 2-thiopyrimidine And 2-oxindole

The allylation of Morita-Baylis-Hillman(MBH)carbonates is one of the important methods to construct multifunctional compounds and can be used to construct C-C,C-N,C-O,C-P and C-S bonds.It has been widely used in organic synthesis because of its characteristics of high efficiency,convenient and simple operation.In recent years,though the S-allylation reaction involving MBH carbonates has been studied,less research has been done on the reactions of heterocyclic nucleophiles both containing of N and S heteroatoms.2-Thiopyrimidine,a special conjugate heterocycle,has wide application in the fields of pharmacology and material chemistry.Therefore,it is of scientific and academic significance to explore the S-allylation of 2-thiopyrimidine with MBH carbonates.Michael reaction is one of the most classic reactions in organic synthesis,and the study of Michael reaction is more comprehensive.In recent years,the cascade reactions that combined the simple Michael reaction with other type reactions got more and more attention from organic synthesis workers.2-Oxindole can be widely used in the synthesis of drugs and natural products,and 1,4-diketones are a kind of very important organic synthesis intermediates.Thus,base catalyzed Michael addition-oxidation-ring-cleavage reacton of ?,?-unasaturated ketones and 2-oxindole to synthesize of 1,4-diketones has certain innovation and potential application values,and the method has not been reported before.Based on the literature,we mainly studied the DABCO catalyzed S-allylation of MBH carbonates and 2-thiopyrimidine.At the same time,the base-catalyzed Michael addition-oxidation-ring-cleavage reaction of ?,?-unasaturated ketones with 2-oxindole was systematically studied.The thesis is divided into two parts,a total of four chapters:Part I: S-allylic alkylation of 2-thiopyrimidine with MBH carbonatesChapter 1: 2-Thiopyrimidine and progress in allylation of MBH carbonatesThis chapter summarizes the application of 2-thiopyrimidine compounds in the fields of pharmaceuticals,materials chemistry and inorganic chemistry,and theallylation of MBH carbonates.It focuses on the progress of the allylation reaction of MBH carbonates to construct C-C,C-N and C-S bonds.Chapter 2: S-Allylic alkylation of 2-thiopyrimidine and MBH carbonatesWe developed a new method that DABCO-catalyzed selective S-allylic alkylation of 2-thiopyrimidine with MBH carbonates.Though the method is not ideal for some other sulfur-containing heterocycles,for 2-thiopyrimidine,it shows excellent chemoselectivity and regioselectivity and has merits of high yield,mild conditions,broad scope of substrate and simple operation.Part II: Michael addition-oxidation-ring-cleavage reaction of 2-oxindole and ?,?-unasaturat-ed ketonesChapter 3: 2-oxindole and its progress of Michael addition reaction and synthesis of 1,4-diketonesIn this chapter,the synthesis and application of medcines and natural products with 2-oxindole fragment has been introduced.In addition,the progress of the Michael reaction of 2-oxindole and the the ways of synthesis of 1,4-diketones are reviewed in detail.Chapter 4: Michael addition-oxidation-ring-cleavage reaction of 2-oxindole with ?,?-unasaturated ketonesIn this chapter,we have completely studied the base-catalyzed Michael addition-oxidation-ring cleavage reaction of 2-oxindole with ?,?-unasaturated ketones.By screening the base,solvent,reaction temperature and amount of base,the desired products were obtained in moderate yield under the optiomal reaction conditions.Most importantly,the method provides a novel strategy for the synthesis of the 1,4-diketones while producing a new amino group at the ortho position of the substituent,which has a good potential application value.