Functionalized MCM-41-supported Copper Complexes Catalyzed Carbon-carbon Bond And Carbon-heteroatom Bond Formation Reactions

1. MCM-41-immobilized bidentate nitrogen copper(I) chloride complex(MCM-41-2N-Cu Cl) was prepared starting from commercially available and inexpensive 3-(2-aminoethylamino)propyltrimethoxysilane via immobilization on MCM-41, followed by the reaction with Cu Cl. The MCM-41-2N-Cu Cl complex was characterized by XRD, ICP and elemental analysis. We investigated the crosscoupling reaction of terminal alkynes with thiophenols catalyzed by MCM-41-2N-Cu Cl in DMSO with K2CO3 as base under oxygen atmosphere. The results showed that the MCM-41-2N-Cu Cl complex exhibited high catalytic activity and could be reused many time without significant loss of activity, which providing a new green route to the synthesis of alkynyl sulfides.2. We explored the A3 reaction of tetrahydroisoquinoline(THIQ), aldehydes and alkynes in the presence of MCM-41-immobilized bidentate nitrogen copper(I) iodide(MCM-41-2N-Cu I) and 4 ? molecular sieves in toluene. It was found that the MCM-41-2N-Cu I complex could catalyze the A3 reaction effectively and be reused several times without any loss of catalytic activity, which providing a new, practical and green method for the preparation of a variety of C1-alkynylated tetrahydroisoquinolines.3. A novel MCM-41-immobilized tridentate nitrogen copper(I) complex(MCM-41-3N-Cu I) was conveniently prepared starting from commercially available and inexpensive 3-(2-aminoethylamino)propyltrimethoxysilane via immobilization on MCM-41, followed by reacting with pyridine-2-carboxaldehyde and Cu I. We investigated the cascade reaction of 2-halobenzoic acids and amidines catalyzed by MCM-41-3N-Cu I complex in DMF with Cs2CO3 as base. The results showed that this heterogeneous copper catalyst exhibited high catalytic activity and could be reused many times without significant loss of activity, which providing a new green route to the synthesis of a variety of quinazolinone derivatives.4.(4-Chloromethylphenyl)trichlorosilane reacted with MCM-41 gave chloromethyl-functionalized MCM-41(MCM-41-CH2Cl). The latter underwent the condensation with N-Boc-4-hydroxy-L-proline and deprotection to afford L-prolinefunctionalized MCM-41(MCM-41-L-Proline). The MCM-41-immobilized Lproline copper(I) chloride complex(MCM-41-L-Proline-Cu Cl) and copper(I) bromide complex(MCM-41-L-Proline-Cu Br) were prepared by the reaction of the MCM-41-L-Proline with Cu Cl or Cu Br, respectively. We investigated their catalytic properties in the halogenation reactions of arylboronic acids with NCS or NBS in acetonitrile. The results showed that both MCM-41-L-Proline-Cu Cl and MCM-41-L-Proline-Cu Br exhibited high catalytic activity, generating a variety of aryl chlorides or bromides in good to excellent yields and could be reused many times without any loss of catalytic activity.