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The substituent redistribution of hydrosilanes on silicon through C-Si and Si-H bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective C-Si/Si-H bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(C6F5)3. This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes. [ABSTRACT FROM AUTHOR]

Our calculations found that the O∴O three-electron (3e) bonds (2.16∼2.27 Å) can be formed not only between two neighboring peptide units in a main chain but also between two adjacent peptide units in two different main chains in proteins. This finding may address electron hole migration from one peptide unit to the next in proteins. Evidently, stability of the O∴O 3e bonded species is strongly dependent on the component of the oligopeptides and is reduced owing to the steric hindrance of the side chains when the big chains present in oligopeptides. Besides, formation of the O∴O 3e bonds competes with the formation of the other forms of three-electron bonds depending on the component of the polypeptides. Formation of the O∴S 3e bond is thermodynamically more favorable than that of the O∴O 3e bond for the oligopeptides containing sulfur atom in their side chains. Similarly, formation of the O∴π 3e bond between aromatic ring of the side chain and the neighboring peptide unit is more stable than that of the O∴O 3e bond when the aromatic amino acids present in the oligopeptides. We infer that a series of three-electron bonds may be formed during the electron hole migration along the peptide backbone in proteins and assist electron hole transport as relay stations, supporting the peptide chain as a conduction wire. The ab initio molecular dynamics simulations of the polypeptides also support this conclusion. [ABSTRACT FROM AUTHOR]

The combination of palladium acetate with XPhos shows high efficiency in the Hiyama cross-coupling reactions of aryl mesylates with arylsilanes. The reactions proceed smoothly to generate the corresponding biaryl compounds in good yields. [ABSTRACT FROM AUTHOR]

Pd-catalyzed Suzuki—Miyaura cross-coupling reaction of aryl tosylates with potassium aryl trifluoroborate in the presence of bulky and electron-rich phosphine ligand is described. In addition, a useful chemoselective coupling of an aryl chloride in the presence of a tosyloxy group was demonstrated. [ABSTRACT FROM AUTHOR]

Metal-free catalytic C–H silylation of a series of aromatic compounds such as N,N-disubstituted anilines with various hydrosilanes has been achieved for the first time using commercially available B(C6F5)3 as a catalyst. This protocol features simple and neutral reaction conditions, high regioselectivity, wide substrate scope (up to 40 examples), Si–Cl bond compatibility, and no requirement for a hydrogen acceptor. [ABSTRACT FROM AUTHOR]

The branching copolymerization of styrene with triethylene glycol dimethacrylate (tri-EGDMA) as the branching agent was carried out using atom transfer radical polymerization (ATRP) in anisole at 90 °C. The resulting copolymers were analyzed using 1H NMR and triple detection size exclusion chromatography (TD-SEC). The NMR analysis shows that the pendent vinyl groups react even in the early stages of the polymerization. Analysis of the changes in the molecular weight and polydispersity of the copolymers suggests that the reaction system contains three components: the primary chains, the slightly branched chains comprising of two primary chains, and the highly branched chains consisting of more than three primary chains. The coupling reaction mainly takes place between the primary chains, resulting in the slightly branched chains in the early stages of the reaction, the weight fraction of the branched chains and the degree of branching increase gradually with monomer conversion, highly branched chains mainly form at relatively high monomer conversions. [ABSTRACT FROM AUTHOR]