24667-94-5Relevant articles and documents
An open metal site metal-organic framework Cu(BDC) as a promising heterogeneous catalyst for the modified Friedl?nder reaction
Phan, Nam T.S.,Nguyen, Tung T.,Nguyen, Khoa D.,Vo, Anh X.T.
, p. 128 - 135 (2013)
A crystalline porous metal-organic framework Cu(BDC) was synthesized, and characterized by several techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), atomic absorption spectrophotometry (AAS), hydrogen temperature-programmed reduction (H2-TPR), and nitrogen physisorption measurements. The Cu(BDC) exhibited high catalytic activity for the modified Friedl?nder transformation using 2-aminobenzyl alcohol as the starting material, thus offering advantages over the conventional Friedl?nder reaction in terms of avoiding the problems associated with the storage of the highly unstable 2-aminobenzaldehyde. Moreover, the Cu(BDC) could offer significantly higher catalytic activity than that of other Cu-MOFs such as Cu3(BTC) 2, Cu(BPDC), and Cu2(BDC)2(DABCO). The catalyst could be recovered and reused several times without a significant degradation in catalytic activity. The modified Friedl?nder reaction could only occur in the presence of the solid Cu(BDC) with no contribution from leached active species.
Bioinspired Radical-Mediated Transition-Metal-Free Synthesis of N-Heterocycles under Visible Light
K. Bains, Amreen,Ankit, Yadav,Adhikari, Debashis
, p. 324 - 329 (2020/11/30)
A redox-active iminoquinone motif connected with π-delocalized pyrene core has been reported that can perform efficient two-electron oxidation of a class of substrates. The design of the molecule was inspired by the organic redox cofactor topaquinone (TPQ), which executes amine oxidation in the enzyme, copper amine oxidase. Easy oxidation of both primary and secondary alcohols happened in the presence of catalytic KOtBu, which could reduce the ligand backbone to its iminosemiquinonate form under photoinduced conditions. Moreover, this easy oxidation of alcohols under aerobic condition could be elegantly extended to multi-component, one-pot coupling for the synthesis of quinoline and pyrimidine. This organocatalytic approach is very mild (70 °C, 8 h) compared to a multitude of transition-metal catalysts that have been used to prepare these heterocycles. A detailed mechanistic study proves the intermediacy of the iminosemiquinonate-type radical and a critical hydrogen atom transfer step to be involved in the dehydrogenation reaction.
Zinc Stabilized Azo-anion Radical in Dehydrogenative Synthesis of N-Heterocycles. An Exclusively Ligand Centered Redox Controlled Approach
Das, Siuli,Mondal, Rakesh,Chakraborty, Gargi,Guin, Amit Kumar,Das, Abhishek,Paul, Nanda D.
, p. 7498 - 7512 (2021/06/30)
Herein we report an exclusively ligand-centered redox controlled approach for the dehydrogenation of a variety of N-heterocycles using a Zn(II)-stabilized azo-anion radical complex as the catalyst. A simple, easy-to-prepare, and bench-stable Zn(II)-complex (1b) featuring the tridentate arylazo pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline, in the presence of zinc-dust, undergoes reduction to form the azo-anion radical species [1b]- which efficiently dehydrogenates various saturated N-heterocycles such as 1,2,3,4-tetrahydro-2-methylquinoline, 1,2,3,4-tetrahydro-isoquinoline, indoline, 2-phenyl-2,3-dihydro-1H-benzoimidazole, 2,3-dihydro-2-phenylquinazolin-4(1H)-one, and 1,2,3,4-tetrahydro-2-phenylquinazolines, among others, under air. The catalyst has further been found to be compatible with the cascade synthesis of these N-heterocycles via dehydrogenative coupling of alcohols with other suitable coupling partners under air. Mechanistic investigation reveals that the dehydrogenation reactions proceed via a one-electron hydrogen atom transfer (HAT) pathway where the zinc-stabilized azo-anion radical ligand abstracts the hydrogen atom from the organic substrate(s), and the whole catalytic cycle proceeds via the exclusive involvement of the ligand-centered redox events where the zinc acts only as the template.
