Design and Synthesis of Zirconium‐Containing Coordination Polymer Based on Unsymmetric Indolyl Dicarboxylic Acid and Catalytic Application on Borrowing Hydrogen Reaction

Abstract

Catalytic borrowing hydrogen reaction is a very attractive transformation in the field of Calkylation reaction. In this work, a new Zr (Zirconium)-containing coordination polymer containing unsymmetric indolyl dicarboxylic acid 1-(carboxymethyl)-1H-indole-5-carboxylic acid (H 2 CIA) was synthesized by the way of a solvothermal synthetic route and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Nitrogen adsorption-desorption, fourier transform infrared spectroscopy and X-ray photoelectronic spectroscopy (XPS). The coordination polymer Zr-CIA was employed as the catalyst for C-alkylation of acetophenone derivatives in the presence of benzyl alcohol. In addition, Zr-CIA catalyst was also observed to be effective in the reaction of alcohols with alcohols and high yields of alkylation products were achieved. Mechanism investigations were also conducted to better understand the catalysts and transformations. Meanwhile, the Zr-CIA could be reused at least five times without a notable decrease in activity and selectivity.

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

“…3‐(4‐chlorophenyl)‐1‐(4‐methoxyphenyl) propan‐1‐one (3 bc) Yield 241.8 mg 88 % (Catalyst Ru1 ), 247.3 mg 90 % (Catalyst Ru2 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.92 (d, J =8.8 Hz, 2H), 7.24 (d, J =8.3 Hz, 2H), 7.16 (d, J =8.4 Hz, 2H), 6.91 (d, J =9.0 Hz, 2H), 3.85 (s, 2H), 3.21 (t, J =7.6 Hz, 2H), 3.01 (t, J =7.6 Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 197.55, 163.60, 139.99, 131.87, 130.43, 130.14, 128.66, 113.84, 55.57, 39.88, 29.63.…”

“…3‐(3,4‐dimethoxyphenyl)‐1‐(p‐tolyl)propan‐1‐one (3 db) Yield 255.9 mg 90 % (Catalyst Ru1 ), 261.6 mg 92 % (Catalyst Ru2 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (d, J =8.2 Hz, 2H), 7.20 (d, J =7.8 Hz, 2H), 6.76 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.22 (t, J =7.6 Hz, 2H), 2.97 (t, J =8.0 Hz, 2H), 2.36 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 199.07, 148.97, 147.45, 143.87,134.51, 134.10, 129.35, 128.23, 120.27, 111.95, 111.44, 56.01, 55.93, 40.60, 29.96, 21.69.…”

A Zirconium Indazole Carboxylate Coordination Polymer as an Efficient Catalyst for Dehydrogenation‐Cyclization and Oxidative Coupling Reactions

“…When Zr-CIA catalyst [32] was initially used to synthesize the biologically active benzimidazole derivatives in this work, results observed were not ideal (Scheme 3), which might be caused by the low activity of zirconium when binding with indole-skeleton ligand. Several nitrogen containing ligands were subsequently evaluated in order to produce the best zirconium catalysts in terms of stability and catalytic activity.…”

“…However, studies regarding the catalytic activity of zirconium complexes in dehydrogenative cyclization are extremely rare. Inspired by Zr-catalyzed borrowing hydrogen reactions previously developed in our group, [32] we used this newly developed Zr-IDA to catalyze the synthesis of 1,2disubstituted benzimidazole. Interestingly, this economically synthesized Zr catalyst exhibited high efficiency in borrowing dehydrogenative cyclizations, affording 1,2-disubstituted benzimidazole derivatives in high yields.…”

Crystal Structures, Hirshfeld Surfaces, and Thermal Study of Isostructural Polymeric Ladders of La(III) and Sm(III) Coordination Compounds with 4,4’-Bipyridine and Dibromoacetates

“…These compounds find applications in many different areas of everyday life, industry, and science. Some of the examples are sensors and biosensors [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ], electronic and optoelectronic devices [ 9 , 10 ], chemical catalysts, and photocatalysts [ 11 , 12 , 13 , 14 , 15 , 16 ]. Some coordination polymers can be used to remove harmful substances [ 17 , 18 , 19 , 20 ] or to capture and entrap other molecules [ 21 , 22 ].…”