Effective cyanosilylation of aldehydes with copper(II)-based polymeric catalysts

• Published in: Molecular catalysis Vol. 428; pp. 17 - 23
• Main Authors: Ma, Zhen, Gurbanov, Atash V., Sutradhar, Manas, Kopylovich, Maximilian N., Mahmudov, Kamran T., Maharramov, Abel M., Guseinov, Firudin I., Zubkov, Fedor I., Pombeiro, Armando J.L.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-03-2017
• Subjects: Arylhydrazone linker; CuII coordination polymers; Cyanosilylation of aldehydes; Homogeneous catalysis; Non-covalent interactions; Zwitterionic complexes; CuII coordination polymers; Cyanosilylation of aldehydes; Arylhydrazone linker; Homogeneous catalysis; Zwitterionic complexes; Non-covalent interactions
• ISSN: 2468-8231; 2468-8231
• DOI: 10.1016/j.molcata.2016.11.036

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•Copper(II) zwitterionic coordination polymers as effective catalysts for cyanosilylation of aldehydes.•Reaction assisted by non-covalent interactions (cation-π and tetrel bondings).•High yield of cyanohydrin trimethylsilyl ethers is achieved in methanol at room temperature.•Catalytic properties can be tuned by varying organic linkers in coordination polymers.
The new 1D copper(II) coordination polymers (CPs) [Cu(μ-L1)(H2O)]n (1, H2L1=2-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)benzoic acid) and [Cu(μ-H2L2)(H2O)]n (2, H4L2=(Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)terephthalic acid) and the known zwitterionic 1D CP [Cu2(H2O)2(μ-H2L3)(μ-L3)]n (3, H3L3=2-(2-(4,4-dimethyl-2,6-dioxocyclo-hexylidene)hydrazinyl)terephthalic acid) were synthesized and tested as homogeneous catalysts for cyanosilylation of a variety of aldehydes to the corresponding cyanohydrin trimethylsilyl ethers. Among these polymeric catalysts, 3, with a zwitterionic charater, is the most effective one, giving 86–99% yield of the ethers upon reaction of aliphatic and aromatic aldehydes with trimethylsilyl cyanide in methanol at room temperature in 4h. Non-covalent interactions (cation-π and tetrel bondings) involving the aldehyde substrate are proposed to assist the cyanosilylation reaction.