Indole-3-thio­uronium nitrate

In the title compound, C9H10N3S+·NO3 −, the indole ring system and the thiouronium group are nearly perpendicular, with a dihedral angle of 88.62 (6)°. Hydrogen bonding generates two-dimensional networks which are linked to each other via π stacking inter­actions of the indole groups [average inter-planar ring–ring distance of 3.449 (2) Å]

Palladium nanoparticles confined in thiol-functionalized ordered mesoporous silica for more stable Heck and Suzuki catalysts

Palladium nanoparticles of similar size of ~2 nm were synthesized on different silica-based materials, all functionalized with thiol groups i.e., Aerosil-380, SBA-15, plugged SBA-15 and m-MCF. The resulting materials were used to study the influence of the confinement of Pd nanoparticles in a functionalized silica support on the Heck and the Suzuki reactions. In the case of the Heck reaction, for all catalysts it was proven that leached Pd species were responsible for the activity. However, the catalysts based on ordered mesoporous silica were still able to restrict Pd particle growth, giving rise to an enhanced stability. For the Suzuki reaction, stronger alkaline conditions were required and catalysts based on plugged SBA-15 showed a higher stability than those based on SBA-15 and m-MCF, which both collapsed after the first cycle. At almost identical Pd particle size, ordered mesoporous materials enhance stability and particle growth is slowed down but not fully suppressed

Indole-3-thio­uronium iodide

In the title compound, C9H10N3S+·I−, the indole ring system and the thiouronium group are essentially perpendicular, with a dihedral angle of 89.87 (8)°. By inter­molecular hydrogen bonding, a three-dimensional network is formed, which is additionally supported by inter­molecular C—H⋯π inter­actions

Artificial Metalloenzymes for Hydrogenation and Transfer Hydrogenation Reactions

The development of artificial hydrogenases (AHases) and transfer hydrogenases (ATHases) has played a leading and guiding role for the field of artificial metalloenzymes. Starting from the early studies by Whitesides and coworkers, this chapter showcases the conceptual development of AHases and ATHases, highlighting the different conjugation strategies used for their construction and exemplifying the stereoselective control in product formation that can be reached

Artificial Metalloenzymes for Hydrogenation and Transfer Hydrogenation Reactions

The development of artificial hydrogenases (AHases) and transfer hydrogenases (ATHases) has played a leading and guiding role for the field of artificial metalloenzymes. Starting from the early studies by Whitesides and coworkers, this chapter showcases the conceptual development of AHases and ATHases, highlighting the different conjugation strategies used for their construction and exemplifying the stereoselective control in product formation that can be reached

N,N,O-Coordinated tricarbonylrhenium precatalysts for the aerobic deoxydehydration of diols and polyols

Rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass-derived polyols using L4Re(CO)3 as precatalyst (L4Re(CO)3 = tricarbonylrhenium 2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)(methyl)amino)methyl)phenolate). The DODH reaction was optimized using 2 mol% of L4Re(CO)3 as precatalyst and 3-octanol as both reductant and solvent under aerobic conditions, generating the active high-valent rhenium species in situ. Both diol and biomass-based polyol substrates could be applied in this system to form the corresponding olefins with moderate to high yield. Typical features of this aerobic DODH system include a low tendency for the isomerization of aliphatic external olefin products to internal olefins, a high butadiene selectivity in the DODH of erythritol, the preferential formation of 2-vinylfuran from sugar substrates, and an overall low precatalyst loading. Several of these features indicate the formation of an active species that is different from the species formed in DODH by rhenium-trioxo catalysts. Overall, the bench-top stable and synthetically easily accessible, low-valent NNO–rhenium complex L4Re(CO)3 represents an interesting alternative to high-valent rhenium catalysts in DODH chemistry. Graphical abstract: N,N,O-Coordinated tricarbonylrhenium precatalysts for the aerobic deoxydehydration of diols and polyol

A Cp‐based Molybdenum Catalyst for the Deoxydehydration of Biomass‐derived Diols

Dioxo‐molybdenum complexes have been reported as catalysts for the deoxydehydration (DODH) of diols and polyols. Here, we report on the DODH of diols using [Cp*MoO2]2O as catalyst (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl). The DODH reaction was optimized using 2 mol % of [Cp*MoO2]2O, 1.1 equiv. of PPh3 as reductant, and anisole as solvent. Aliphatic vicinal diols are converted to the corresponding olefins by [Cp*MoO2]2O in up to 65 % yield (representing over 30 turnovers per catalyst) and 91 % olefin selectivity, which rivals the performance of other Mo‐based DODH catalysts. Remarkably, cis‐1,2‐cyclohexanediol, which is known as quite a challenging substrate for DODH catalysis, is converted to 30 % of 1‐cyclohexene under optimized reaction conditions. Overall, the mass balances (up to 79 %) and TONs per Mo achievable with [Cp*MoO2]2O are amongst the highest reported for molecular Mo‐based DODH catalysts. A number of experiments aimed at providing insight in the reaction mechanism of [Cp*MoO2]2O have led to the proposal of a catalytic pathway in which the [Cp*MoO2]2O catalyst reacts with the diol substrate to form a putative nonsymmetric dimeric diolate species, which is reduced in the next step at only one of its Mo‐centers before extrusion of the olefin product

The B(C6F5)3-Catalyzed Tandem Meinwald Rearrangement-Reductive Amination

A system of three coupled catalytic cycles enabling the one-pot transformation of epoxides to amines via Meinwald rearrangement, imine condensation, and imine reduction is described. This assisted tandem catalysis is catalyzed by B(C6F5)3 resulting in the first tandem Meinwald rearrangement-reductive amination protocol. The reaction proceeds in nondried solvents and yields β-functionalized amines. In particular, β-diarylamines are obtained in high yields