Cyanosilylation by Compounds with Main-Group Elements: An Odyssey

Abstract

The past few decades have seen remarkable headways in the structural and reaction chemistry of compounds with heavier main-group elements. In recent years, there is an ongoing effort to derive catalytic chemistry involving main-group compounds, driven by their lower costs and higher terrestrial abundances. Here, a survey on the state-of-the-art in the development of cyanosilylation methodology by compounds with heavier main-group elements has been given. Once dominated by transition metals, the field has matured to embrace the majority of the main-group elements including aluminum, silicon, and calcium. Of particular focus will be how the mechanism of cyanosilylation involving compounds with main-group elements differs from those of transition metals.

Substrate, Catalyst, and Solvent: The Triune Nature of Multitasking Reagents in Hydroboration and Cyanosilylation

“…Leung and co-workers reported the successful cyanosilylation of aldehyde with TMSCN in the absence of solvent and catalyst, with benzaldehyde as the substrate. As for the case of hydroboration, we have considered the possibility that the presence of an additional TMSCN molecule can affect the kinetics of the reaction favorably.…”

“…There is an important, environmentally beneficial area of research that has seen impressive growth in recent years. This pertains to the field of solvent-free and external-catalyst-free chemistry. − The current work, employing both computational and experimental approaches, aims to provide a mechanistic understanding of this chemistry. Specifically, we have explored two important functionalization reactions: hydroboration and cyanosilylation.…”

“…“The best catalyst is no catalyst” sums up the need for green processes in the current age, and it is gratifying to see the increasing application of this dictum to a wider and wider variety of chemical reactions, including hydroboration, − cyanosilylation, , acetalization, and the aza-Michael addition . However, in order for this to become even more of an important area of development, it is necessary to understand and establish the principles on which this chemistry is founded.…”

Heavier Tetrylenes as Single Site Catalysts

“…Recently, p-block compounds have emerged as potential catalysts and are being utilized by several research groups for various type of homogeneous catalytic reactions. [4][5][6] Through design of ligand with appropriate sterics and electronics, it is possible to control and fine-tune the reactivity and catalytic property of several well-defined p-block compounds. In the domain of catalysis usually p-block compounds with their usual and thermodynamically stable oxidation state such as Al(III), Si(IV) etc.…”

“…However, now owing to the toxicity, less abundance and higher cost expenditure the synthetic chemists are shifting their focus towards more economical and easy accessible catalysts as viable alternatives to transition metal catalysts for similar organic transformations. Recently, p ‐block compounds have emerged as potential catalysts and are being utilized by several research groups for various type of homogeneous catalytic reactions [4–6] . Through design of ligand with appropriate sterics and electronics, it is possible to control and fine‐tune the reactivity and catalytic property of several well‐defined p ‐block compounds.…”