Organosilicon-Mediated Organic Synthesis (SiMOS): A Personal Account

Abstract

The organosilicon-mediated organic synthesis (SiMOS) has attracted much attention over the recent decades. However, the use of organosilicon reagents with novel catalytic strategies remains to be explored. This Account summarizes our group’s progress mainly based on the application of a wide variety of organosilicon reagents, including allylic silanes, trifluoromethyl silane, acylsilanes, chlorosilanes, hydrosilanes, trimethylsilyldiazomethane, trimethylsiloxyfuran, silanols, α-trimethylsilylmethylacetate, and trimethylsilylcyanide, in catalysis and organic reactions. These transformations were proved to be alternative procedures for the construction of structurally diverse compounds.1 Introduction2 The Exploration of New Reactivity of Organosilicon Reagent in Organic Synthesis2.1 Allylic Silanes2.2 Trifluomethylsilane (TMSCF3)2.3 Acylsilanes2.4 Chlorosilanes and Hydrosilanes2.5 Trimethylsilyldiazomethane (TMSD)2.6 Trimethylsiloxyfuran2.7 Silanols2.8 Trimethylsilylcyanide (TMSCN)3 Conclusion and Perspective

Catalytic regio- and stereoselective silicon–carbon bond formations on unsymmetric gem-difluorocyclopropenes by capture of silyl metal species

“…This work provides new examples of the synthetic values of organofluorine or organosilicon compounds based on the silicon–carbon bond cleavage or silicon–carbon bond-forming process and related fields of palladium/copper catalysis. It is hoped that the precise control of the fluorine effect on silicon-mediated organic synthesis (SiMOS) will provide guidance for applying this strategy of SiMOS 23 for the discovery of new transition metal-promoted transformations in both organosilicon and fluorine chemistry.…”

Recent Advances in the Synthesis of Acylsilanes

“…However, these processes are transitively dependent on the limited transition metal catalysis, and there are certain restrictions on the substrate range, such as the retention of active functional groups. The investigation of the reaction mechanism is not thorough enough, and further exploration is needed . In the choice of starting materials, the concise and efficient methods for synthesizing acylsilanes with readily available compounds have been rarely reported.…”

Rhodium-Catalyzed Chemodivergent Synthesis of Organosilicons Enabled by Controllable C–Si Bond Activation

“…Organosilicons have been regarded as an important class of organic compounds because of their versatility as building blocks in organic synthesis and wide applications in materials science. , Additionally, the unique properties of silicon make organosilicons highly attractive in drug discovery . Therefore, significant efforts have been dedicated to the improvement and development of approaches to the efficient construction of organosilicon compounds .…”