Mechanistic Studies on the Gas‐Phase Dehydrogenation of Alkanes at Cyclometalated Platinum Complexes

In the ion/molecule reactions of the cyclometalated platinum complexes [Pt(L? H)]⁺ (L=2,2′‐bipyridine (bipy), 2‐phenylpyridine (phpy), and 7,8‐benzoquinoline (bq)) with linear and branched alkanes C_nH_2n+2 (n=2–4), the main reaction channels correspond to the eliminations of dihydrogen and the respective alkenes in varying ratios. For all three couples [Pt(L? H)]⁺/C₂H₆, loss of C₂H₄ dominates clearly over H₂ elimination; however, the mechanisms significantly differs for the reactions of the “rollover”‐cyclometalated bipy complex and the classically cyclometalated phpy and bq complexes. While double hydrogen‐atom transfer from C₂H₆ to [Pt(bipy? H)]⁺, followed by ring rotation, gives rise to the formation of [Pt(H)(bipy)]⁺, for the phpy and bq complexes [Pt(L? H)]⁺, the cyclometalated motif is conserved; rather, according to DFT calculations, formation of [Pt(L? H)(H₂)]⁺ as the ionic product accounts for C₂H₄ liberation. In the latter process, [Pt(L? H)(H₂)(C₂H₄)]⁺ (that carries H₂ trans to the nitrogen atom of the heterocyclic ligand) serves, according to DFT calculation, as a precursor from which, due to the electronic peculiarities of the cyclometalated ligand, C₂H₄ rather than H₂ is ejected. For both product‐ion types, [Pt(H)(bipy)]⁺ and [Pt(L? H)(H₂)]⁺ (L=phpy, bq), H₂ loss to close a catalytic dehydrogenation cycle is feasible. In the reactions of [Pt(bipy? H)]⁺ with the higher alkanes C_nH_2n+2 (n=3, 4), H₂ elimination dominates over alkene formation; most probably, this observation is a consequence of the generation of allyl complexes, such as [Pt(C₃H₅)(bipy)]⁺. In the reactions of [Pt(L? H)]⁺ (L=phpy, bq) with propane and n‐butane, the losses of the alkenes and dihydrogen are of comparable intensities. While in the reactions of “rollover”‐cyclometalated [Pt(bipy? H)]⁺ with C_nH_2n+2 (n=2–4) less than 15 % of the generated product ions are formed by C? C bond‐cleavage processes, this value is about 60 % for the reaction with neo‐pentane. The result that C? C bond cleavage gains in importance for this substrate is a consequence of the fact that 1,2‐elimination of two hydrogen atoms is no option; this observation may suggest that in the reactions with the smaller alkanes, 1,1‐ and 1,3‐elimination pathways are only of minor importance.     

Efficient Tandem Synthesis of Methyl Esters and Imines by Using Versatile Hydrotalcite‐Supported Gold Nanoparticles

Efficient basic hydrotalcite (HT)‐supported gold nanoparticle (AuNP) catalysts have been developed for the aerobic oxidative tandem synthesis of methyl esters and imines from primary alcohols catalyzed under mild and soluble‐base‐free conditions. The catalytic performance can be fine‐tuned for these cascade reactions by simple adjustment of the Mg/Al atomic ratio of the HT support. The one‐pot synthesis of methyl esters benefits from high basicity (Mg/Al=5), whereas moderate basicity greatly improves imine selectivity (Mg/Al=2). These catalysts outperform previously reported AuNP catalysts by far. Kinetic studies show a cooperative enhancement between AuNP and the surface basic sites, which not only benefits the oxidation of the starting alcohol but also the subsequent steps of the tandem reactions. To the best of our knowledge, this is the first time that straightforward control of the composition of the support has been shown to yield optimum AuNP catalysts for different tandem reactions.     

CO2 on a Tightrope: Stabilization,Room‐Temperature Decarboxylation,and Sodium‐Induced Carboxylate Migration

A sterically shielded 3‐substituted zwitterionic N,N‐dimethylisotryptammonium carboxylate has been synthesized by consecutive chemoselective double alkylation of indole. The carboxylate undergoes a quantitative and unusually facile decarboxylation in dimethyl sulfoxide (DMSO) or dimethyl formamide (DMF) at room temperature. The breaking of a nearly equidistant hydrogen bond by solvent molecules initiates heterolytic C? C cleavage. The decarboxylation rate decreases with increasing CO₂ partial pressure, proving the competitiveness of protonation and re‐carboxylation of the carbanionic intermediate. Corresponding spiro compounds containing silylene and stannylene moieties show high thermal stability. Addition of an excess of methyllithium to the sodium salt triggers a reaction sequence comprising a deprotonation, carboxylate transfer, and nucleophilic trapping of the rearranged carboxylate by another equivalent of methyllithium. Hydrolytic work‐up of the geminal diolate leads to an acetyl product. The role of the sodium counterion and the mechanism of the rearrangement have been unraveled by deuteration experiments.     

Reversible and Efficient Inhibition of UDP‐Galactopyranose Mutase by Electrophilic,Constrained and Unsaturated UDP‐Galactitol Analogues

A series of UDP‐galactitols were designed as analogues of high‐energy intermediates of the UDP‐galactopyranose mutase (UGM) catalyzed furanose/pyranose interconversion, an essential step of Mycobacterium tuberculosis cell wall biosynthesis. The final compounds structurally share the UDP and the galactitol substructures that were connected by four distinct electrophilic connections (epoxide, lactone and Michael acceptors). All molecules were synthesized from a common perbenzylated acyclic galactose precursor that was derivatized by alkenylation, alkynylation and cyclopropanation. The inhibition study against UGM could clearly show that slight changes in the relative orientation of the UDP and the galactitol moieties resulted in dramatic variations of binding properties. Compared to known inhibitors, the epoxide derivative displayed a very tight, reversible, inhibition profile. Moreover, a time‐dependent inactivation study showed that none of these electrophilic structures could react with UGM, or its FAD cofactor, the catalytic nucleophile of this still intriguing reaction.     

Formal Total Synthesis of Palmerolide A

A formal total synthesis of the 20‐membered marine macrolide, palmerolide A from chiral pool tartaric acid is described. Elaboration of a γ‐hydroxy amide, which is derived from the desymmetrization of tartaric acid amide, and Boord olefination are the pivotal reactions employed for the synthesis of the chiral building blocks, and Stille coupling and ring‐closing metathesis (RCM) are used to assemble the macrolactone.     

Optical Properties and Photo‐Oxidation of Tetraphenylethene‐Based Fluorophores

We report the optical properties of tetraphenylethene (TPE) and other TPE derivatives functionalised with an octyl group (TPE‐OCT) and polyethyleneglycol group (TPE‐PEG) in the side chain. We compared TPE‐OCT and TPE‐PEG with TPE in both organic solvents and under aqueous conditions. All materials exhibit aggregation‐induced emission, however, uncommonly, TPE‐PEG seems to aggregate in aqueous solution with enhanced photoluminescence quantum efficiency (PLQE) relative to that in organic solvents. All three materials can be photo‐oxidised in solution to their diphenylphenanthrene derivative by irradiation with UV light (at both ≈1 and ≈5 mW cm^?2), with a subsequent enhancement in PL efficiency. The electron‐donating ether group increases the rate of oxidation relative to bare TPE and also photo‐oxidation was shown to be solvent and concentration dependent. Finally, photo‐oxidation was also demonstrated in the aggregate state.     

Pd‐Catalyzed Reaction of Allyl Carbonate with Polyols: The Role of CO2 in Transesterification versus Etherification of Glycerol

An intermolecular Pd/PPh₃‐catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first‐order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. ¹³C isotopic labeling studies demonstrate that the Pd‐catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO₂ in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate η¹‐ and η³‐allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N₂ or CO₂ could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity.     

Heterotermetallic Indium Lithium Halostannates: Low‐Temperature Single‐Source Precursors for Tin‐Rich Indium Tin Oxides and Their Application for Thin‐Film Transistors

The syntheses and structural elucidation of dimeric [Sn(OCyHex)₂] ( 1 ), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)₃Sn}₂] (M=Li ( 2 ), Na ( 3 ), K ( 4 )), and of the first heteroleptic heterotermetallic Li/In/Sn–haloalkoxide clusters [X₂In{LiSn₂(OCyHex)₆}] (X=Br ( 5 ), Cl ( 6 )) with a double seco‐norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin‐rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy‐dispersive X‐ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin‐containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2θ values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In₂O₃ lattice and partially occupied In³⁺ sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin‐film field‐effect transistors (FETs) were fabricated by spin‐coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25–700 °C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge‐carrier mobility of 6.36×10^?1 cm² V^?1 s (calcination at 250 °C) and an on/off current ratio of 10⁶.     

Comparison of the Peroxidase‐Like Activity of Unmodified,Amino‐Modified,and Citrate‐Capped Gold Nanoparticles

The origin of the peroxidase‐like activity of gold nanoparticles and the impact of surface modification are studied. Furthermore, some influencing factors, such as fabrication process, redox property of the modifier, and charge property of the substrate, are investigated. Compared to amino‐modified or citrate‐capped gold nanoparticles, unmodified gold nanoparticles show significantly higher catalytic activity toward peroxidase substrates, that is, the superficial gold atoms are a contributing factor to the observed peroxidase‐like activity. The different catalytic activities of amino‐modified and citrate‐capped gold nanoparticles toward 3,3′,5,5′‐tetramethylbenzidine (TMB) and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) diammonium salt (ABTS) show that the charge characteristics of the nanoparticles and the substrate also play an important role in the catalytic reactions.     

Asymmetric Nucleophilic Monofluorobenzylation of Carbonyl Compounds: Synthesis of Enantiopure vic‐Fluorohydrins and α‐Fluorobenzylketones

Asymmetric nucleophilic monofluoroalkylation of a broad range of aldehydes with an α‐fluoro‐γ‐sulfinylbenzyl carbanion takes place with complete control of the facial selectivity at the carbanion and good to high anti‐diastereoselectivity to give easily separable mixtures of two optically pure 1,2‐fluorohydrin derivatives (up to 24:1 anti/syn). Separation and removal of the p‐tolylsulfinyl group with tBuLi provides enantiomerically pure anti‐1,2‐disubstituted‐1,2‐fluorohydrins, whereas α‐fluorobenzylketones can be obtained by desulfinylation of the mixture followed by pyridinium chlorochromate oxidation (one‐pot process).