Synthesis Of MCM-41-immobilized L-proline Copper(Ⅰ) Complexes And Their Applications In C-N Bond Formation Reactions

1.(4-Chloromethylphenyl)trichlorosilane was reacted with mesoporous MCM-41 in toluene,followed by treatment with EtOH to give chloromethyl-functionalized MCM-41(MCM-41-CH2Cl).The latter underwent the condensation with N-Boc-4-hydroxy-L-proline and deprotection to afford L-proline-functionalized MCM-41(MCM-41-L-Proline).The MCM-41-immobilized L-proline copper(I)iodide complex(MCM-41-L-Proline-CuI)was prepared by the reaction of the MCM-41-L-Proline with CuI in actone and characterized.We investigated its catalytic properties in the cascade reaction of aryl iodides with amidine hydrochlorides in DMF leading to a variety of primary arylamines.The results showed that MCM-41-L-Proline-CuI complex exhibited good catalytic activity in this C–N bond formation reaction,and could be reused at least 8 times without any loss of catalytic activity,providing a novel,practical and green route to primary arylamines.2.The MCM-41-immobilized L-proline copper(I)chloride complex(MCM-41-L-Proline-CuCl)was prepared by the reaction of the MCM-41-L-Proline with CuCl in acetone.We investigated its catalytic properties in the reaction of arylboronic acids with sulfonyl azides in methanol leading to a variety of N-arylsulfonamides.The results showed that MCM-41-L-Proline-CuCl complex exhibited excellent catalytic activity in this C–N coupling reaction,and could be recycled at least 8 times without any loss of catalytic activity,providing an efficient and practical route to a variety of N-arylsulfonamides.3.The MCM-41-immobilized L-proline copper(I)bromide complex(MCM-41-L-Proline-CuBr)was prepared by the reaction of MCM-41-L-Proline with CuBr in acetone.We investigated its catalytic properties in the annulation reaction of 2-halobenzamides with benzylamines or heteroarylmethylamines leading to a variety of quinazolinone derivatives.The results showed that the MCM-41-L-Proline-CuBr catalyst exhibited high catalytic activity,and coulld be recycled at least 6 times without any loss of catalytic activity,providing a novel and green method for construction of a variety of quinazolinone derivatives.4.We investigated catalytic properties of MCM-41-immobilized L-proline copper(I)iodide complex(MCM-41-L-Proline-CuI)in the tandem three component reaction of 2-aminopyridines,acetophenones with benzyl cyanide in NMP leading to a variety of 3-cyanoimidazo[1,2-a]pyridines.The results showed that MCM-41-L-Proline-CuI complex exhibited higher catalytic activity than homogeneous CuI and could be reused for six times without any loss of catalytic activity,providing a novel,practical and green method for the synthesis of a variety of 3-cyanoimidazo[1,2-a]pyridines.