Recent Advances in Transition-Metal-Catalyzed Synthetic Transformations of Organosilicon Reagents

Abstract

Organosilicon compounds act as a nucleophile upon activation by an appropriate base and behave in a manner similar to main-group organometallic reagents. In the last decades, structurally divergent organosilicon reagents are available and have become more employed for synthetic transformation with the aid of transition-metal complexes, because organosilicon compounds are in general superior to other organometallic compounds in view of stability, solubility, nontoxicity, and easy-handling. Particularly, cross-coupling of organosilicon reagents with organic halides or pseudohalides has been considered to be a useful tool for constructing the carbon frameworks of various target molecules such as pharmaceuticals and π-conjugated functional materials. Perfluoroalkylsilicon compounds such as CF3SiEt3 have found use as reagents for the metal-catalyzed introduction of perfluoroalkyl groups into many substrates. In addition, functionalized organosilicon reagents are readily accessible by catalytic approach starting with appropriate hydrocarbons such as alkenes, alkynes, alkanes, and arenes. This article reviews recent advances in transition-metal-catalyzed transformations of organosilicon reagents according to the type of synthetic transformation and metal catalyst.

Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process

“…Based on previous reports and our experimental evidence, a plausible reaction mechanism is depicted in Scheme 4. In the first step, Ag I is oxidized to an Ag II species, and the continuity of the redox reactions led to the formation of phenylmethanimine (5), and again the combination of redox and hydrolysis reac-tion led to the formation of benzamide (10) and benzaldehyde (6). The formation of benzaldehyde, benzamide, and benzoic acid (7) was unequivocally detected during GC measurements, and can also be seen in the reaction time-profile in the earlier stages of the reaction (Figure 2).…”

Mechanism on The Disproportionating Synthesis of Dichlorodimethyl‐ silane by ZSM‐5(5 T)@γ‐Al2O3 Series Core‐Shell Catalysts

“…They have basic properties such as low surface tension, low viscosity coefficient, high compressibility and high gas permeability, also have excellent properties such as high and low temperature resistance, electrical insulation, resistance to oxidation stability and physiological inertness. They are widely used in aerospace, electrical and electronics, construction, medical and other industries . With the continuous growth of the number and variety of organic silicon, the application market has been continuously expanded to form an important product system unique to the chemical new materials industry, and demand for them is likewise increasing.…”

Mechanism of Enolate Transfer between Si and Cu

“…Silylated enolates are used as latent nucleophiles in many reactions, and their activation is induced through Lewis acids or bases . In the case of base activation, Si−O bond breaking leading to transfer of the enolate to a copper (or more generally metal) complex is proposed . This can be formally described as a chain transfer between Si and Cu in which enolate exchanges with an X group whose nature depends on the exact reaction at stake.…”

“…[1] In the case of base activation,S i ÀOb ond breaking leadingt ot ransfer of the enolatet oacopper( or more generally metal) complex is proposed. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] This can be formally described as ac hain transferb etween Si and Cu in which enolate exchanges with an Xg roup whose nature depends on the exact reaction at stake. For instance, in the case of the coppercatalyzed asymmetric vinylogousM ukaiyamaa ldol (Cu-CAVM) reaction, [21] which has been at the origin of our studies, ad ienolate transfer from at rimethylsilyl (TMS)m oiety to aC u I complex is proposed to form aC u-bonded nucleophile (Scheme 1).…”