RESUMO
Ruthenium-triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox-neutral C-C bond cleavage of the ß-O-4 lignin linkage of 1,3-dilignol model compounds. A mechanistic pathway involving a dehydrogenation-initiated retro-aldol reaction for the C-C bond cleavage was proposed in line with experimental data and DFT calculations.
RESUMO
The combination of phosphorus(V)-based Lewis acids with diaryl amines and diaryl silylamines promotes reversible activation of dihydrogen and can be further exploited in metal-free catalytic olefin hydrogenation. Combined experimental and density functional theory (DFT) studies suggest a frustrated Lewis pair type activation mechanism.
RESUMO
The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H2] or the cationic intermediate [Ru(Triphos)(Solvent)(H)(H2)](+) in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to CâO groups and C-O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H2] and [Ru(Triphos)(µ-H)]2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources.
RESUMO
A series of aryl-difluorophosphoranes are converted to give fluorophosphonium salts [Ph2PF(o-C6X4BR2)](+) (X = H, F; R = Cy, Mes). The proximity of the two weakly Lewis acidic fluorophosphonium and borane moieties results in enhanced Lewis acid catalytic reactivity.
RESUMO
Terminal and internal alkynes are efficiently hydroborated to (E)-alkenyl pinacol boronic esters with excellent yields and selectivities using a Lewis acid catalyst. In the case of Piers' borane (HB(C6F5)2) the borane acts as a pre-catalyst generating dissymmetrically gem-diborylated species of the form RCH2CR'(Bpin)(B(C6F5)2) which are the active catalysts.