Cyanosilylation of Carbonyl Compounds with Trimethylsilyl Cyanide Catalyzed by an Yttrium‐Pillared Silicotungstate Dimer

Abstract

Ein Yttrium‐verbrücktes Silicowolframat‐Dimer (siehe Bild) katalysiert die Cyanosilylierung von Ketonen und Aldehyden mit Trimethylsilylcyanid (TMSCN). Die Reaktionen verlaufen selektiv und geben die entsprechenden Cyanhydrintrimethylsilylether. Die katalytische Aktivität des Dimers ist vor allem für Aldehyde beeindruckend, mit einer Umsatzzahl von 18 000 und einer Umsatzfrequenz von 540 000 h−1 für n‐Hexanal.

1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

“…However, due to the toxicity and difficulties in handling of HCN, a number of alternative cyanating reagents with less harmful and easily manageable properties have been subsequently introduced 1 2 3 4 . Among other cyanating reagents, TMSCN is one of the most accessed reagents for cyanohydrins synthesis, allowing them to be prepared as cyanohydrin trimethylsilyl ethers 1 2 3 4 7 8 9 10 11 12 13 14 . In this respect, the development of efficient catalysts for the addition of TMSCN to carbonyl compounds has been the focal research point.…”

“…In this respect, the development of efficient catalysts for the addition of TMSCN to carbonyl compounds has been the focal research point. As a consequence, various Lewis acids, Lewis bases, metal alkoxides, as well as inorganic salts have been successfully employed in promoting this transformation 3 12 13 14 15 16 17 18 19 20 21 22 23 24 .…”

Immobilization of LaW10 onto Ionic‐Liquid‐Modified Mesoporous Silica: Deep Desulfurization with Zero‐Order Reaction Kinetics

“…[32,33] Among the large number of POM motifs, rare-earthcontaining POMs offer interesting features owing to the relatively large ionic radii, high coordination numbers, and flexible coordination geometries of rare-earth cations, which could leave open coordination sites as effective Lewis acids for the activation of substrates. [32,33] Among the large number of POM motifs, rare-earthcontaining POMs offer interesting features owing to the relatively large ionic radii, high coordination numbers, and flexible coordination geometries of rare-earth cations, which could leave open coordination sites as effective Lewis acids for the activation of substrates.…”

“…It is known that POMs can be regarded as excellent oxygen donor ligands, and that metal substitution into POMs is one of the most promising approaches for creating catalytically active sites. [32,33] Among the large number of POM motifs, rare-earthcontaining POMs offer interesting features owing to the relatively large ionic radii, high coordination numbers, and flexible coordination geometries of rare-earth cations, which could leave open coordination sites as effective Lewis acids for the activation of substrates. [32,33] In addition, the nucleophilic surfaces with large negative charges allow POMs to act as Lewis bases and/or stabilizers of cationic reaction intermediates.…”

A new heterometallic MOF with 1D nano-sized channels for cyanosilylation reaction and prevention effect against arrhythmia by reducing the sympathetic excitability

“…Hence, it is a hot issue in the society of chemistry to find the catalysts with high effective for carbonyl compounds cyanosilication catalyzed by TMSCN. In recent decades, a lot of the homogeneous catalysts, such as N-heterocyclic carbenes, inorganic or organic salts, Lewis bases and Lewis acids, can catalyze reaction, they have been widely researched [14,15]. Nevertheless, the reactions of homogeneous catalytic usually require painstaking steps of purification, so in recent years, research direction in the field are mainly focused on the use of the heterogeneous catalysts, particularly MOFs, at the aim of overcoming the problem of product catalyst separation at the conditions of without solvent [16][17][18].…”