Silicon Compounds Mediated Formylation And Trifluoromethylation

Organosilicon compounds are one of the important types of element-organic compounds,including silane,silanol and silyl ether,which have been applied in many reactions.In this thesis,trimethoxysilane（（MeO）₃SiH）and trifluoromethyltrimethylsilane（TMSCF₃）have been applied in the N-formylation reaction of aniline or amine compounds and the trifluoromethylthiolation reaction respectively.Green chemistry involves catalysis,organic synthesis,analytical chemistry and other disciplines,with a wide range of contents.N-formylation of amine compounds has a wide range of applications in drug synthesis and chemical products.The synthesis of traditional amine compounds often requires the use of highly toxic and environmentally unfriendly formylation reagents.In this thesis,CO₂ is used to replace the traditional formylation reagent,and hydrosilane is used as the hydrogen source for hydrosilylation.The series formylation reaction of amine compounds can generate corresponding formylation products with high selectivity,which is in line with the concept of green chemistry.In the second chapter,the synthesis and characterization of a series of PNP-type ligands were introduced in detail,and the low temperature formylation reaction of amine with CO₂ and（MeO）₃SiH was co-catalyzed with Cu salt.The results showed that the optimal ratio of metal salt Cu（OAc）₂ to polyether chain PNP ligand L1 in the catalytic system was 1:1,the amount of catalyst was5.0 mol%,and toluene was used as solvent.The N-formylation reaction of amine with CO₂ and（MeO）₃SiH could be catalyzed at 30 ^oC for 2 hours,and the formylation product was obtained with high yield.The secondary amine and alkyl amine could be formylated,and the yield of formylation product could reach 84.0%.Trifluoromethylgroup has extremely high lipophilic performance parameters,and its introduction into drug molecules can improve its physical and chemical properties as a drug.In the third chapter,a series of N-thiophthalimides were synthesized and used to prepare trifluoromethyl sulfide by perfluoroalkylation with TMSCF₃.The results showed that in the reaction process,DMSO（1.0 M）was used as solvent,Na OAc（3.0 equiv）as activator,and TMSCF₃（3.0 equiv）reacted at room temperature for 1 hour,the yield of trifluoromethyl sulfide reached 91.2%,and the reaction was compatible with alkyl and aryl substrates.