Abstract
Organosilicon compounds are highly important molecular scaffolds with versatile synthetic
utility, and are used in a range of transformations. Such organosilicon compounds
are employed in a wide range of research areas, including medicinal chemistry, drug
discovery, pharmaceuticals, agrochemicals, fine chemicals, etc. Moreover, they are
commonly encountered in a number of commercial products. However, the preparation
of organosilicon compounds by means of traditional methods significantly limit their
wider applications. Recently, several new concepts and powerful methods have been
developed in order to prepare organosilicon compounds via transition-metal catalysis
or without metal catalysis. While many procedures have been reported for the silylation
of aromatic systems, methods for the silylation of heteroarenes are scarce. Nevertheless
several excellent and robust strategies for heteroarene silylation have been discovered.
In this short review, we summarize the different methods, mechanisms and catalyst
development for the regioselective silylation of heteroarenes.
1 Introduction
2 Silylation of C–H Bonds through Organometallic Intermediates
2.1 Intermolecular C–H Bond Silylation Assisted by Directing Groups
2.2 Undirected Intermolecular C–H Bond Silylation
2.3 Intramolecular C–H Bond Silylation via a Tethered Silyl Unit
3 C–H Bond Silylation with Silicon Electrophiles
4 C–H Bond Silylation with Silicon Nucleophiles
5 C–H Bond Silylation with Silyl Radicals
6 Other Approaches
6.1 Alkali-Metal-Catalyzed C–H Bond Silylation
6.2 Magnesium-Promoted Reductive C–H Bond Silylation
7 Conclusions and Outlook
Key words
heteroarenes - silylation - functionalization - regioselectivity - C–H bond activation
- silicon electrophile - silicon nucleophile - silyl radical
