Adrian Franczyk

(E)-9-(2-iodovinyl)-9H-carbazole: a new coupling reagent for the synthesis of π-conjugated carbazoles.

The one-pot synthesis of (E)-9-(2-iodovinyl)-9H-carbazole via sequential ruthenium-catalyzed silylative coupling of N-vinylcarbazole with vinyltrimethylsilane and iododesilylation is reported. Its use as a new building block in the palladium-catalyzed Sonogashira and Suzuki-Miyaura coupling reactions to yield new carbazole-containing (E)-but-1-en-3-ynes and (E,E)-buta-1,3-dienes is demonstrated.

Silsesquioxyl rhodium(I) complexes - synthesis, structure and catalytic activity

The first bi- and mononuclear rhodium(I) complexes [{Rh(μ-OSi(8)O(12)(i-Bu)(7))(cod)}(2)] (5), [Rh(cod)(PCy(3))(OSi(8)O(12)(i-Bu)(7))] (6) with a hindered hepta(iso-butyl)silsesquioxyl ligand bonded to the rhodium(I) center through Rh-O-Si bonds have been synthesized and their structures have been solved by spectroscopic methods and X-ray analysis. Their exemplary catalytic properties in silylative coupling of vinylsilanes with styrene are also presented.

A highly selective synthesis of new alkenylsilsesquioxanes by hydrosilylation of alkynes

Hydrosilylation of a wide group of mono- and disubstituted (symmetrical and nonsymmetrical) alkynes with 1-dimethylsiloxy-3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.13,9.15,15.17,13]octasiloxane ((HSiMe2O)(i-Bu)7Si8O12, 1) in the presence of Karstedts catalyst (Pt2(dvs)3) has been performed for the first time. A series of new 1,2-(E)-disubstituted and 1,1,2-(E)-trisubstituted ethenes with a silsesquioxane moiety were selectively afforded and fully characterized. On the basis of nuclear magnetic resonance (NMR) and infrared spectroscopy (in situ FT-IR and/or FT-IR), the influence of alkyne structure and reaction conditions on the stereoselectivity as well as on the progress of triple bond hydrosilylation catalyzed by Pt2(dvs)3 was explained. The results of the studies clearly indicated for which reagents the developed procedures lead to alkenylsilsesquioxanes with almost stoichiometric yields in short time, and for which other catalytic systems or methods should be considered.

An effective catalytic hydroboration of alkynes in supercritical CO2 under repetitive batch mode

A facile method for the synthesis of unsaturated organoboron compounds by hydroboration of terminal and internal alkynes in supercritical (sc) CO2 has been presented for the first time. The reactions performed in scCO2 in the presence of Ru catalysts (selectivity, productivity) are compared with those in a traditionally used solvent or without it. Moreover, the catalytic systems based on the application of scCO2 have been successfully tested for the processes under repetitive batch conditions. This strategy permitted us to obtain boryl‐substituted olefins with high yields and selectivities up to the 16th catalytic cycle if using Ru(CO)Cl(H)(PPh3)3 as a catalyst. The process applied the self‐dosing catalyst, which is gradually released to the reaction mixture under supercritical conditions in the individual batch. Such an approach has a positive impact on process sustainability and economy.

Synthesis of Functionalized Silsesquioxanes as Molecular Templates for Hybrid Materials

Abstract Polyhedral oligomeric silsesquioxanes with a rigid inorganic Si–O–Si core and flexible, reactive, and/or inert organic coronae have attracted much attention. Their unique structures, in addition to their physical properties made them important due to their possible use as precursors and components of versatile inorganic/organic hybrid materials. This chapter presents a short overview of selected procedures to obtain functionalized silsesquioxanes.

Selective Hydrosilylation of Alkynes with Octaspherosilicate (HSiMe2O)8Si8O12

Comprehensive studies on platinum-catalyzed hydrosilylation of a wide range of terminal and internal alkynes with spherosilicate (HSiMe2 O)8 Si8 O12 (1 a) were performed. The influence of the reaction parameters and the types of reagents and catalysts on the efficiency of the process, which enabled the creation of a versatile and selective method to synthesize olefin octafunctionalized octaspherosilicates, was studied in detail. Within this work, twenty novel 1,2-(E)-disubstituted and 1,1,2-(E)-trisubstituted alkenyl-octaspherosilicates (3 a-m, 6 n-t) were selectively obtained with high yields, and fully characterized (1 H, 13 C, 29 Si NMR, FTIR, MALDI TOF or TOF MS ES+ analysis). Moreover, the molecular structure of the compound (Me3 Si(H)C=C(H)SiMe2 O)8 Si8 O12 (3 a) was determined by X-ray crystallography for the first time. The developed procedures are the first that allow selective hydrosilylation of terminal silyl, germyl, aryl, and alkyl alkynes with 1 a, as well as the direct introduction of sixteen functional groups into the 1 a structure by the hydrosilylation of internal alkynes. This method constituted a powerful tool for the synthesis of hyperbranched compounds with a Si-O based cubic core. The resulting products, owing to their unique structure and physicochemical properties, are considered novel, multifunctional, hybrid, and nanometric building blocks, intended for the synthesis of star-shaped molecules or macromolecules, as well as nanofillers and polymer modifiers. In the presented syntheses, commercially available reagents and catalysts were used, so these methods can be easily repeated, rapidly scaled up, and widely applied.