The ?-C-H Functionalization Of ?-Amino Carbonyl Compounds And AIBN Promoted Oxidation Recyclization Of 1H?Indoles

This paper mainly discussed the?-C-H functionalization of?-aminocarbonyl compounds and the oxidative recyclization reaction of 1H?Indoles.The research progresses on the?-C-H activation of?-amino carbonyl compounds,the application of carbon tetrabromide in organic reactions and the synthesis of benzoxanthines are described.This paper included these six chapters:Chapter 1:The studies on the?-C-H functionalization of?-aminocarbonyl compounds via oxidative coupling reactions.?-Aminocarbonyl compounds are important structural motifs existing widely in natural products and therapeutic agents.The functionalization of?-C-H bonds of?-aminocarbonyl compounds has attracted considerable attention in organic and bioorganic synthesis.This chapter mainly introduces the progress on?-C-H activation of?-amino carbonyl compounds to form C?sp³?-C?sp²?/C?sp³?-C?sp³?bonds and C-heterobonds.These methods provide diverse pathways for the?-C-H functionalization of?-aminocarbonyl compounds and enrich the use of?-amino carbonyl compounds in organic synthesis chemistry.Chapter 2:Application of carbon tetrabromide in organic synthesis.Carbon tetrabromide,as a commercially available and cheap reagent,has found many applications in organic synthesis,for example,it has been used for the bromination of various functional groups,such as alcohols?Appel reaction?,N-heterocycles,ethers,and for converting aldehydes/ketones into 1,1-dibromo-alkenes or alkynes?Corey–Fuchs reaction?.In addition,carbon tetrabromide is a highly efficient catalyst for versatile reactions,including acylation of phenols,alcohols and thiols,acetalization and tetrahydropyranylation and oxidation of aromatic methyl ketones or alkenes to carboxylic acids under very mild conditions.This chapter mainly summarizes the two major appliacation of carbon tetrabromide in organic synthesis:carbon tetrabromide as a brominating reagent for the bromination of various compounds and as the non-metallic catalyst to promote the oxidative coupling reactions.Chapter 3:Copper-catalyzed C-N bond formation via oxidative cross-coupling of amines with?-aminocarbonyl compounds.In this chapter,we described the reaction of Cu?OAc?₂-promoted?-C-H functionalization reaction of?-aminocarbonyl compound to build C-N bond.This procedure employs Cu?OAc?₂/Et₃N catalytic system to achieve the oxidative cross-coupling of amines with?-aminocarbonyl compounds,affording a series of amino substituted?-iminocarbonyl compounds in good yields.Moreover,by slightly modifying the reaction conditions,this transformation could selectively 2-amino-2-oxocarbonyl compounds.This strategy provides a novel route for the?-C-H activation of?-aminocarbonyl compounds.Chapter 4:CBr₄-mediated cross-coupling reactions of?-amino carbonyl compounds with alcohols and thiols to build C–O and C–S bonds,respectively.This chapter mainly present the non-metallic catalyst CBr₄-mediated cross-coupling reactions of?-amino carbonyl compounds with alcohols and thiols to build C–O and C–S bonds,respectively.The reactions were realized under transition-metal-free conditions,providing a eco-friendly way for the?-C-H functionalization of?-aminocarbonyl compounds.Chapter 5:The development on the synthetic methods of benzoxazinones.Benzoxazinones are some of the most important fused heterocycles in many biological compounds and pharmaceutical drugs.Compounds possessing this ring own a variety of biological effects including anticancer,anti-HIV,antiviral andantibacterial activities.Among the different methodologies developed for their preparation,the oxidative cyclization of anthranilic acid,or N-acylanthranilic acid are the most accepted.In this chapter,we summarized the methods for synthesizing benzoxazinones from five aspects and provided a variety of strategies for the synthesis of benzoxazinones.Chapter 6:Oxidative recyclization of 1H?indoles for synthesis of2?indolylbenzoxazinones via cleavage of the C2-C3 bond promoted by AIBN.This chapter demonstrated the C2-C3 bond oxidative cleavage of 1H-indoles in the reaction system of AIBN/PivOH,followed by recyclization to synthesize 2-indolylbenzoxazinone.This metal-free reaction is both atom-and step-efficient,providing an easily available starting materials,simple operation,and mild reaction conditions route for the synthesis of 2?indolylbenzoxazinones.Moreover,this is the first example of constructing benzoxazinones from easily available unprotected indole derivatives through a one-pot method.