MCM-41-Supported Copper Complexes-Catalyzed Construction Of Carbon-Nitrogen And Carbon-Sulfur Bonds

In this dissertation,we describe application of the MCM-41-supported copper complexes in construction of carbon-nitrogen and carbon-sulfur bonds.The research work is mainly divided into three parts as follows:1.The heterogeneous cascade addition-oxidative cyclization of nitriles with2-aminopyridines or amidines was investigated by using a 1,10-phenanthroline-functionalized MCM-41-supported copper（I）complex[Phen-MCM-41-CuBr]as the catalyst and air as the oxidant.The results indicated that the heterogeneous copper-catalyzed cascade reaction proceeded smoothly in 1,2-dichlorobenzene or DMSO at120-130oC,yielding a wide variety of 1,2,4-triazole derivatives in mostly high yields.This heterogeneous copper（I）catalyst could be facilely prepared via a two-step proce-dure from commercially readily available and inexpensive reagents and exhibited higher catalytic activity than the CuBr/1,10-Phen system.Phen-MCM-41-CuBr was also easy to recover and was recyclable up to eight times with almost consistent activity.2.MCM-41-supported Schiff base-pyridine bidentate copper（II）complex[MCM-41-Sb,Py-Cu（OAc）₂]was prepared and characterized by different physico-chemical techniques.We investigated oxidative coupling reaction of oxime acetates and sodium sulfinates by using MCM-41-Sb,Py-Cu（OAc）₂ as the catalyst and oxime acetates as an internal oxidant to provide an efficient and practical route toβ-keto sulfones.The results indicated that the heterogeneous copper-catalyzed oxidative coupling reaction proceeded smoothly in toluene at 100oC,followed by hydrolysis,affording a variety ofβ-keto sulfones in good to excellent yields.This new hetero-geneous copper（II）catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu（OAc）₂.The MCM-41-Sb,Py-Cu（OAc）₂ complex could be recovered by a simple filration and recycled up to eight times without significant loss of activity.3.We investigated cascade three component reaction of terminal alkynes,diazo esters and amines by using an MCM-41-supported 1,10-phenanthroline-copper（I）complex[Phen-MCM-41-CuI]as catalyst to prepare（E）-β-enamino esters.The results indicated that this heterogeneous copper-catalyzed cascade three component reaction of terminal alkynes,diazo esters and amines proceeded smoothly in toluene at 100oC,affording a variety of（E）-β-enamino esters in high yields.This supported copper catalyst could be recovered by fitration of reaction mixture and recycled at least 8times with almost consistent activity.