Visible-light-catalyzed Reaction Of Sulfonyl Radicals With Olefins

As an abundant,readily available,environment-friendly and sustainable green energy source,visible light has become increasingly concerned.And it has been successfully applied by chemists in the field of organic synthesis chemistry.With the aid of photocatalysts,light energy is converted to chemical energy by the pathways of atom transfer,energy transfer or single electron transfer,so that organic molecules can indirectly the energy of visible light to complete a series of reactions.Currently,visible-light catalysis has become one of the significant development areas in organic chemistry.Especially,the strategy of forming free radical intermediates by single electron transfer pathway,accomplishing the purpose that other catalytic methods are difficult to achieve,and showing its unique chemical reactivity.The second chapter mainly concentrates on the synthesis of sulfonated isoquinolinediones by the way of the addition/cyclization of sodium sulfinate and acrylamide derivatives,in which sulfonyl radicals can be accessed from simple sodium sulfinates under visible light and eosin Y catalysis.Isoquinolinedione derivatives are found in numerous natural products and drug molecules.To date,the radical addition/cyclization synthesis of complex organic structural fragments is definitely the efficient synthesis strategy with higher atom economy.Firstly,N-methacryloyl-N-methylbenzamide and sodium benzenesulfinate were employed as substrates for the model reaction.The amounts of water,molar ratio of substrates,the types of photocatalysts,photocatalyst loading and light source were screened to obtain the optimized reaction conditions.Secondly,the substrate scope of the reaction was explored and 27 sulfonylated isoquinolinedione derivatives were prepared in a medium yields.Finally,the plausible mechanism of the reaction was explored by control experiments including radical trapping and fluorescence quenching experiments.The investigation in this section is a useful supplement to the existing synthesis of sulfonated isoquinolinediones.The third chapter mainly discusses the sequence hydroxylation sulfonylation of allylacetamide derivatives mediated by visible-light catalysis to synthesize ?-hydroxysulfone compounds in one pot.?-hydroxysulfone compounds have important biological activity and medicinal value,and are important research objects in many fields such as chemistry and biology.It is an effective method to synthesize complicated organic molecules by introducing different functional groups into the same molecular mediated by visible light in one pot.First,N-phenyl-N-(2-phenylallyl)acetamide and benzenesulfinic acid were chosen as substrates for the model reaction.Then,types and loading of photocatalyst,solvents,types and loading of additive,molar ratio of substrates and light source were screened for the optimized reaction conditions.Subsequently,20 ?-hydroxysulfone compounds were prepared under the optimized reaction conditions in medium yields.Moreover,the possible mechanism of this reaction was proposed based on radical trapping and fluorescence quenching experiments.Research in this section provides a mild,facile and eco-friendly tactic for difunctionalization of olefins.