Removable bidentate directing group assisted-recyclable metal–organic frameworks-catalyzed direct oxidative amination of Sp 2 C–H bonds

Auxiliary-directed etherification of sp2 C–H bonds under heterogeneous metal–organic framework catalysis: synthesis of ethenzamide

“…Surprisingly, other previously commonly used Cu-MOFs in cross coupling reactions failed to provide sufficient amount of products (entries 2-6). [27][28][29] This could be rationalized by the exceptional large aperture pore size of Cu-MOF-74, especially when starting materials possess large molecular size. Magnetic nanoparticle CuFe 2 O 4 as well as traditional Cu/zeolite or Cu/ZSM-5 were showed to be inefficient (entries [7][8][9].…”

C–H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions

“…Jana has reported the copper­(II)-mediated C­(sp 2 )–H amination of aminoquinoline benzamides with challenging electron-rich aniline derivatives . A similar amination reaction was reported by Truong using a heterogeneous Cu-MOF catalyst and N -methyl morpholine oxide (NMO) as an oxidant . We optimized our reaction conditions and were delighted to find that the amination works under milder conditions than the amidation, in toluene at 100 °C for 6 h under an inert atmosphere with a lower catalyst (5 wt % Cu-MnO) loading (15 mg, 4.7 mol % Cu) and without any additives.…”

“…Notably, Yu and co-workers first reported the copper-catalyzed pyridine-directed C–H amination reaction . After that, several groups have successfully reported the Cu-catalyzed C­(sp 2 )–H amination with a different directing group, mostly under homogeneous conditions. − In particular, the 8-aminoquinoline-assisted amination of ortho -C­(sp 2 )–H bonds of benzoic acid derivatives was first reported by Daugulis and co-workers by employing simple Cu­(OAc) 2 as a catalyst and N -methyl morpholine oxide (NMO) as an oxidant in the presence of a Ag 2 CO 3 additive . The same group made an exceptional advancement and reported a more general and efficient method using simple Cu­(OAc) 2 or (CuOH) 2 CO 3 as the catalyst and air as a terminal oxidant with a wide range of amine coupling partners .…”

“…72 A similar amination reaction was reported by Truong using a heterogeneous Cu-MOF catalyst and N-methyl morpholine oxide (NMO) as an oxidant. 75 We optimized our reaction conditions and were delighted to find that the amination works under milder conditions than the amidation, in toluene at 100 °C for 6 h under an inert atmosphere with a lower catalyst (5 wt % Cu-MnO) loading (15 mg, 4.7 mol % Cu) and without any additives. The C−H amination of 8-amino quinoline benzamides with different cyclic and acyclic amines was next investigated under the optimized reaction conditions.…”

Formation of C–C and C–Heteroatom Bonds by C–H Activation by Metal Organic Frameworks as Catalysts or Supports

“…68,69 In one of these examples, the coupling between N-benzoyl-8-amino-quinoline and morpholine was effectively promoted by MOF-199 in 99 % yield using 20% AgOAc with N-methylmorpholine oxide as oxidant in N-methyl pyrrolidine as solvent at 90 o C (Scheme 17). 41 The structure of MOF-199 has been proposed for this transformation promoted by Cu-CPO-27, but, however, further studies are required to validate these assumptions.…”