This review presents the main achievements in the use of the thiol-ene reaction in the chemistry of silicones. Works are considered, starting from monomers and ending with materials.The main advantages and disadvantages of this reaction are demonstrated using various examples. A critical analysis of the use of this reaction is made in comparison with the hydrosilylation reaction.

A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction medium, on the polycondensation process was determined. The molecular weight characteristics and structure of the L-PPSQ elements obtained were determined by GPC, ¹H, ²⁹Si NMR, IR spectroscopy, viscometry, and PXRD methods. The physicochemical properties of L-PPSQs were determined by TGA and mechanical analyses.

This work presents an approach for the preparation of functional hydrosilanes. The essence of the method is a thiol–ene click reaction on vinyl or allylsilanes. In this case, the Si–H bond in the substrate molecule is not affected. The reaction proceeds with radical (AIBN) or UV initiation with yields close to quantitative. This makes it possible to obtain aliphatic, aromatic, carboxyl and alkoxysilyl derivatives of the corresponding silanes. Crystalline tris(3-(phenylthio)propyl) silane was obtained and characterized for the first time. In the case when the thiol–ene reaction leads to the formation of a three-dimensional network, it was possible to obtain Si–H-containing materials – a transparent monolith and an aerogel with a density of 0.26 g ml⁻¹.

New non-crystallizable low-dispersity star-shaped polydimethylsiloxanes (PDMS) containing stereoregular cis-tetra(organo)(dimethylsiloxy)cyclotetrasiloxanes containing methyl-, tolyl- and phenyl-substituents at silicon atoms and the mixture of four stereoisomers of tetra[phenyl(dimethylsiloxy)]cyclotetrasiloxane as the cores were synthesized. Their thermal and viscous properties were studied. All synthesized compounds were characterized by a complex of physicochemical analysis methods: nuclear magnetic resonance (NMR), FT-IR spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), viscometry in solution, rheometry, and Langmuir trough study.