Novel Organosilicon Starburst Compounds Based on Ruthenium-Catalyzed Silylative Coupling Reactions of 1,3,5-Tris(dimethylvinylsilyl)benzene

Abstract

The highly stereo- and regioselective reaction of 1,3,5-tris(dimethylvinylsilyl)benzene (1) with p-substituted styrenes, p-XC6H4CHCH2, where X = H (2), Cl (3), Br (4), vinyl (5), catalyzed by RuHCl(CO)(PCy3)2 (I) appeared to be an efficient basis for new starburst compounds involving silylene−vinylene−arylene sequences. Attempts were made to synthesize the first generation of dendrimer (12), based on 1 as a core, via two methods: direct silylative coupling of 1,3,5-tris[dimethyl(4-vinylstyryl)silyl]benzene (5) with 1, which gave a mixture of oligomers containing the SiCHCHSi structure, and successfully via silylation of 5 with vinylsilyl-3,5-bis(isopropoxysilyl)benzene (10) followed by vinylation with Grignard reagent. Additionally, the double silylation of DVB with 10 followed by vinylation allowed the synthesis of an analogous starburst compound (14), which can be a new core for analogous dendritic compounds.

A new protocol for synthesis of bifunctional alkynyl[vinyl or (E)-alkenyl]substituted organosilicon compounds

“…However, after the 1st step of this process, in the reaction mixture there were always residues of unreacted 5 which was used in excess along with the product (6) and the rest of catalyst (which most of decomposes after the reaction). In consequence, the addition of catalyst and styrenes (8) to the reaction bulb to complete the 2nd step of the synthesis of 9 resulted a mixture of 9 and a product of silylative coupling of 5 with styrenes (reaction known from the literature [15]). In order to avoid silylative coupling of unreacted 5 with styrenes used in the 2nd step of the process, the remains of 5 needed to be evaporated (along with the solvent), leaving the crude product (6) and decomposed catalyst.…”

Highly Stereoselective Synthesis of Arylene‐Silylene‐Vinylene Polymers

“…The catalytic screenings have been carried out in the model catalytic process of vinyldimethylphenylsilane with styrene. [20] The regio-and stereoregular trans-homopolymer 15 was effectively prepared by polycondensation of 11 (monomer which consists of two functional groups: vinylsilyl and styryl) using the very effective and active ruthenium complex 7 as a catalyst, see Scheme 6.…”

Preparation and Diels–Alder reaction of carbosilane dendrimer with conjugated diene

“…1 H NMR (ppm, CDCl 3 ): d = 0.07 (s, 12H, SiMe (G0)), 0.40-0.75 (m, 208H, SiCH 2 (G0), CH 2 (G1, G2)), 1.43-1.88 (m, 1404H, CH 2 (G3), CH 3 (G4)), 3.48-3.78 (m, 312H, OCH 2 (G1, G2, G3)), 4.15-4.39 (m, 648H, OCH 2 (G4)), 5.48-5.78, 5.85-6.30 (m, 1296H, @CH (G4)). 13 C NMR (ppm, CDCl 3 ): d = À1.48 (SiMe (G0)), 1.46, 7.82 (SiCH 2 (G0)), 6.31, 25.71 (CH 2 (G1)), 8.97, 25.65 (CH 2 (G2)), 6.32, 25.79 (CH 2 (G3)), 18.10 (CH 3 (G4)), 63.13 (OCH 2 (G4)), 64.88, 65.14 (OCH 2 (G1, G2, G3)), 128.99, 130.86, 131.04 (@CH (G4)). …”

“…Carbosilane dendrimers were prepared by simple growth methods such as hydrosilation which is well known procedure for the purpose of increasing branches on carbosilane dendrimers [5][6][7][8][9]. And continually the addition of functional groups onto the dendrtic periphery has been established by the reaction between chlorosilyl groups and methalorganyls such as lithiumorganyl as well as Grignard reagent [10,11].…”