Metal Catalyzed C-H Bond Alkylation Of Benzamide Derivatives With The Aid Of Directing Group

C-H bonds are ubiquitous in organic compounds.It would,therefore,appear that direct functionalization of substrates by activation of C-H bonds would eliminate the multiple steps and limitations associated with the preparation of functionalized starting materials.Regioselectivity is an important issue because organic molecules can contain wide variety of C-H bonds.The use of a directing group can largely overcome the issue of regiocontrol by allowing the catalyst to come into proximity with the targeted C-H bonds.Directly alkylation of C-H bonds has always been an important part of C-H activation,and it is also significant to organic synthesis.As O-O bonds of DTBP will break and methyl radical will be generated at high temperature,we successfully achieve Ni and Cu catalyzed ortho-alkylation of benzamide derivatives with 8-aminoquinoline directing groups by making use of methyl radical,which is generated from DTBP.The thesis is divided into three key chapters as follows.(1)We reviewed the development of catalytic functionalization of C(sp2)-H and C(sp3)-H bonds by using bidentate directing groups in the order of different metal catalyst.(2)Ni catalyzed ortho-methylation of benzamide derivatives by using bidentate directing groups is achieved.To obtain an optimized yield,benzamide derivatives are reacted with DTBP while a variety nickel salt,ligands,base,solvent and temperature are used.We finally confirm the best reaction condition as follow:0.3 mmol N-(5-chloroquinolin-8-yl)benzamide(l equiv.)react with 0.6 mmol DTBP(2 equiv.),0.6 mmol Na2CO3(2 equiv.),0.06 mmol Ni(OAc)2(0.2equiv.),0.03 mmol PPh3(0.4 equiv.)in benzotrifluoride at 130?.The scope of this reaction was also extended.(3)Cu catalyzed ortho-alkylation of benzamide derivatives by using bidentate directing groups is achieved.To obtain an optimized yield,benzamide derivatives are reacted with DTBP while a variety copper salt,ligand,base,solvent and temperature are used.We finally confirm the best reaction condition as follow:0.3 mmol N-(quinolin-8-yl)benzamide(1 equiv.)react with 0.6 mmol DTBP(4 equiv.),1.2 mmol K3PO4(4 equiv.),0.15 mmol Cu(OAc)2(0.5 equiv.),in cyclohexane at 130 0C.The scope of this reaction was also extended.