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Heterogenized photoredox catalysts provide a path for sustainable chemical synthesis using highly tunable, reusable constructs. Here, heterogenized iridium complexes as photoredox catalysts were assembled via covalent attachment to metal oxide surfaces (ITO, ZrO2, Al2O3) in thin film or nanopowder constructs. The goal was to understand which materials provided the most promising constructs for catalysis. To do this, reductive dehalogenation of bromoacetophenone to acetophenone was studied as a test reaction for system optimization. All catalyst constructs produced acetophenone with high conversions and yields with the fastest reactions complete in fifteen minutes using Al2O3 supports. The nanopowder catalysts resulted in faster and more efficient catalysis, while the thin film catalysts were more robust and easily reused. Importantly, the thin film constructs show promise for future photoelectrochemical and electrochemical photoredox setups. Finally, all catalysts were reusable 2–3 times, performing at least 1000 turnovers (Al2O3), demonstrating that heterogenized catalysts are a sustainable catalyst alternative. [ABSTRACT FROM AUTHOR]

The article abstracts of various research papers that were recently been published in sister journals of the "Chemistry: A European Journal," including papers on synthesis of lactones, biosynthesis of lactic acid and homogeneous catalysis.

This paper reports on the development of an efficient synthesis of enantiopure phospha[6]helicenes through a [2+2+2] alkyne cyclotrimerization reaction. The corresponding gold complexes proved to be highly efficient both in terms of catalytic activity and enantioselectivity in [2+2] and [4+2] cycloaddition reactions. Furthermore, in the presence of an external nucleophile, such as water or alcohols, the tandem cyclization/addition reactions take place in high yields and excellent diastereo- and enantioselectivities. [ABSTRACT FROM AUTHOR]

The nuclear magnetic resonance (NMR) detectability of several TB‐relevant agents have been significantly improved through the use of the parahydrogen‐based hyperpolarization protocol signal amplification by reversible exchange (SABRE) in conjunction with the 2H‐labelling of key sites within their molecular structures and the 2H‐labelling of the magnetization‐transfer catalyst. The T1 relaxation times and polarization levels of these agents are quantified under test conditions to produce a protocol to identify structurally optimized motifs for future detection in MRI. For more information see the Full Paper by S. B. Duckett et al. on page 16990 ff. [ABSTRACT FROM AUTHOR]

Three new metal-organic porphyrinic framework compounds of zinc and 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) have been synthesized under solvothermal conditions. The compounds [Zn5(C40H24N8)(C8H4O4)2(NO3)6(DMA)2] (DMA)3(H2O)8 ( 1; DMA=dimethylacetamide), [Zn3(C40H24N8)(C8H4O4)2(DMF)](DMF)5(H2O)12 ( 2), and [Zn3(C40H24N8)(C12H6O4)2(DMA)2](H2O)7 ( 3) have two ( 1) and three dimensionally ( 2 and 3) extended structures. All the three structures contain porphyrinic units connected through the carboxylate linkers. The nitrates bind the metal centers and are not hydrogen bonded. The different binding modes of nitrate in the structure of 1 are observed for the first time in a porphyrin-based MOF. The openness of the structure allowed us to explore metal exchange through a room-temperature metathetic route. Compound 2 undergoes 100 % exchange with copper, whereas compound 3 exchanges 70 % with copper. The copper-exchanged compounds Cu∈ 2 and Cu∈ 3 were observed to be good heterogeneous catalysts for many important organic reactions. The chemo and regioselective enamination of β-ketoesters, preparation of propargylamine derivatives as well as regioselective cycloadditions of alkyne and azide (click reactions) have been carried out with good yields and selectivity. All the compounds have been characterized by PXRD, IR, UV/Vis, atomic absorption spectroscopy (AAS), and energy-dispersive X-ray spectroscopy (for Cu exchange). [ABSTRACT FROM AUTHOR]

Gold nanorods (AuNRs) are versatile materials due to their broadly tunable optical properties associated with their anisotropic feature. Conventional seed-mediated synthesis is, however, not only limited by the operational complexity and over-sensitivity towards subtle changes of experimental conditions but also suffers from low yield (≈15 %). A facile seedless method is reported to overcome these challenges. Monodispersed AuNRs with high yield (≈100 %) and highly adjustable longitudinal surface plasmon resonance (LSPR) are reproducibly synthesized. The parameters that influence the AuNRs growth were thoroughly investigated in terms of growth kinetics and soft-template regulation, offering a better understanding of the template-based mechanism. The facile synthesis, broad tunability of LSRP, high reproducibility, high yield, and ease of scale-up make this method promising for the future mass production of monodispersed AuNRs for applications in catalysis, sensing, and biomedicine. [ABSTRACT FROM AUTHOR]

Herein, the effect of diverse metal bromides for the shape evolution of palladium nanostructures (Pd NS) has been demonstrated. Aromaticity-driven reduction of bromopalladate(II) is optimized to reproducibly obtain different Pd NS at the water/organic layer interface. In this soft interfacial strategy, a redox potential driven reaction has been performed, forming the thermodynamically more stable (>104-fold) PdBr42- precursor from PdCl42- by adding extra metal bromides. In the process, the reductant, Hantzsch dihydropyridine ester (DHPE), is aromatized. Interestingly, alkali metal bromides devoid of coordination propensity exclusively evolve Pd nanowires (Pd NWs), whereas in the case of transition metal bromides the metal ions engage the 'N' donor of DHPE at the interface, making the redox reaction sluggish. Hence, controlled Pd nanoparticles growth is observed, which evolves Pd broccolis (Pd NBRs) and Pd nanorods (Pd NRs) at the interface in the presence of NiBr2 and CuBr2 , respectively, in the aqueous solution. Thus, the effect of diverse metal bromides in the reaction mixture for tailor-made growth of the various Pd NS is reported. Among the as-synthesized materials, the Pd NWs stand to be superior catalysts and their efficiency is almost 6 and 2.5 times higher than commercial 20 % Pd/C in the electrooxidation of ethanol and CrVI reduction reaction by formic acid, respectively. [ABSTRACT FROM AUTHOR]

The synthesis and characterisation of several metal complexes of a redox-active, mesityl(Mes)-substituted [1]phosphaferrocenophane, FcPMes ( 1), are reported. Cyclic voltammetry studies on the bimetallic complexes [M(κ1 P- 1)(cod)Cl] (M=Rh: 2; M=Ir: 4), [Rh(κ1 P- 1)2(CO)Cl] ( 3) and [AuCl(κ1 P- 1)] ( 5), in conjunction with DFT calculations, provided indications for a good electronic communication between the metal atoms. To confirm that the ferrocenophane unit might be able to electrochemically influence the reactivity of the coordinated transition metal, the rhodium complex 2 was employed as stimuli-responsive catalyst in the hydrosilylation of terminal alkynes. All reactions were greatly accelerated with in situ generated 2+ as a catalyst as compared to 2. Even more importantly, a markedly different selectivity was observed. Both factors were attributed to different mechanisms operating for 2 and 2+ (alternative Chalk-Harrod and Chalk-Harrod mechanism, respectively). DFT calculations revealed relatively large differences for the activation barriers for 2 and 2+ in the reductive elimination step of the classical Chalk-Harrod mechanism. Thus, the key to the understanding is a cooperative 'oxidatively induced reductive elimination' step, which facilitates both a higher activity and a markedly different selectivity. [ABSTRACT FROM AUTHOR]

The synthesis of alternating donor-acceptor [12] and [16]cycloparaphenylenes (CPPs) has been achieved by the rhodium-catalyzed intermolecular cross-cyclotrimerization followed by imidation and/or aromatization. These alternating donor-acceptor CPPs showed positive solvatofluorochromic properties and smaller HOMO-LUMO gaps compared with nonfunctionalized CPPs, which was confirmed by the theoretical study. [ABSTRACT FROM AUTHOR]

Commercially available BiPh3 was treated with perfluoroalkylphosphinic acids [for example, (C2F5)2P(O)OH] to generate novel, highly Lewis acidic bismuth(III) perfluoroalkylphosphinates of the type Ph xBi[RF2PO2]3− x ( x=0, 1, 2) (RF=-C2F5, -C4F9). The first bismuth(V) perfluoroalkylphosphinate, Ph3Bi[(C2F5)2PO2]2, was synthesized from Ph3BiCl2 and Ag[(C2F5)2PO2]. Examples for the successful application of the catalytically active bismuth(III) and bismuth(V) phosphinates in carbon-carbon bond forming reactions, such as Friedel-Crafts acylation and alkylation, Diels-Alder, Strecker and Mannich reaction, are presented. [ABSTRACT FROM AUTHOR]

Designing zeolites with tunable physicochemical properties can substantially impact their performance in commercial applications, such as adsorption, separations, catalysis, and drug delivery. Zeolite synthesis typically requires an organic structure-directing agent to produce crystals with specific pore topology. Attempts to remove organics from syntheses to achieve commercially viable methods of preparing zeolites often lead to the formation of impurities. Herein, we present organic-free syntheses of two polymorphs of the small-pore zeolite P (GIS), P1 and P2. Using a combination of adsorption measurements and density functional theory calculations, we show that GIS polymorphs are selective adsorbents for H2O relative to other light gases (e.g., H2, N2, CO2). Our findings refute prior theoretical studies postulating that GIS-type zeolites are excellent materials for CO2 separation/sequestration. We also show that P2 is significantly more thermally stable than P1, which broadens the operating conditions for GIS-type zeolites in commercial applications and opens new avenues for exploring their potential use in processes such as catalysis. [ABSTRACT FROM AUTHOR]

The development of inorganic frameworks with extra-large pores (larger than 12-membered rings) has attracted considerable attention because of their potential applications in catalysis, the separation of large molecules, and so forth. We herein report the synthesis of the new extra-large-pore zeolite NUD-2 by using the supramolecular self-assembly of simple aromatic organic cations as structure-directing agents (SDAs). NUD-2 is a high-silicon-content germanosilicate with interconnecting 14×10-membered-ring channels. The SDAs in NUD-2 can be removed by calcination in air at 550 °C to yield permanent pores with a BET surface area of 500 m2g−1. Both germanium and organic cations in NUD-2 can also be removed by treatment with acid at lower temperature, thus not only affording recycling of germanium and SDAs, but also providing a highly stable siliceous zeolite. In addition, aluminum ions can be incorporated into the framework of NUD-2. The NUD-2 structure is yet another extra-large-pore zeolite synthesized by using the supramolecular self-assembling templating approach, thus demonstrating that this approach is a general and applicable strategy for synthesis of new large- and extra-large-pore zeolites. [ABSTRACT FROM AUTHOR]

Medicinally relevant spirocyclic indolenines, carbazoles and quinolines can each be directly synthesised selectively from common indolyl ynone starting materials by catalyst variation. The high yielding, divergent reactions all proceed by an initial dearomatising spirocyclisation reaction to generate an intermediate vinyl-metal species, which then rearranges selectively by careful choice of catalyst and reaction conditions. [ABSTRACT FROM AUTHOR]

A new method has been developed for the synthesis of tetrahydro-2 H-fluorenes based on a Pd(0)-catalyzed benzylic C(sp3)−H functionalization. Importantly, the success of the cyclization step was dependent on there being substituents at the two positions ortho to the benzylic group to avoid an undesired C(sp2)−H functionalization. This method was subsequently used to prepare the right-hand fragment of the hexacyclic triterpenoid benzohopanes, and therefore represents a powerful tool for the construction of the related compounds. [ABSTRACT FROM AUTHOR]

The oxidative metalation method, involving the interaction of free-base meso-triarylcorroles and W(CO)6 in refluxing decalin, led to a set of three tungsten(VI) biscorroles, the first homoleptic sandwich compounds involving corroles. Single-crystal X-ray structures of two of the complexes revealed square-antiprismatic coordination and strongly domed corroles with long W−N distances of 2.15-2.22 Å and a substantial displacement of ∼1.17 Å of the metal relative to the mean N4 planes of the ligands. The structures correspond to approximate C2 symmetry and are thus chiral. DFT calculations strongly indicate that the enantiomers are configurationally stable and hence amenable to chiral resolution. Their other notable properties include a strongly blueshifted Soret band at (357±2) nm, a relatively intense π→W(d [ABSTRACT FROM AUTHOR]

We have described in detail the total synthesis of both the proposed and correct structures of (−)-lyngbyaloside B, which facilitated the elucidation of the complete stereostructure of this natural product. Our study began with the total synthesis of 13-demethyllyngbyaloside B, in which an esterification/ring-closing metathesis (RCM) strategy was successfully used for the efficient construction of the macrocycle. We also established reliable methods for the introduction of the conjugated diene side chain and the l-rhamnose residue onto the macrocyclic framework. However, the esterification/RCM strategy proved ineffective for the parent natural product because of the difficulties in acylating the sterically encumbered C-13 tertiary alcohol; macrolactionization of a seco-acid was also extensively investigated under various conditions without success. We finally completed the total synthesis of the proposed structure of (−)-lyngbyaloside B by means of a macrolactonization that involves an acyl ketene as the reactive species. However, the NMR spectroscopic data of our synthetic material did not match those of the authentic material, which indicated that the proposed structure must be re-examined. Inspection of the NMR spectroscopic data of the natural product and molecular mechanics calculations led us to postulate that the configuration of the C-10, C-11, and C-13 stereogenic centers had been incorrectly assigned in the proposed structure. Finally, our revised structure of (−)-lyngbyaloside B was unambiguously verified through total synthesis. [ABSTRACT FROM AUTHOR]

Assembly of small clusters into rigid bodies with precise shape and symmetry has been witnessed by the significant advances in cluster-based metal-organic frameworks (MOFs), however, nanosized silver cluster based MOFs remain largely unexplored. Herein, two anion-templated silver clusters, CO3@Ag20 and SO4@Ag22, were ingeniously incorporated into a 2D sql lattice ( 1, [CO3@Ag20( iPrS)10(NO3)8(DMF)2] n) and an unprecedented 3D two-fold interpenetrated dia network ( 2, [SO4@Ag22( iPrS)12(NO3)6 ⋅2 NO3] n), respectively, under mild solvothermal conditions. Their atomically precise structures were confirmed by single-crystal X-ray diffraction analysis and further consolidated by IR spectroscopy, thermogravimetric analysis (TGA), and elemental analysis. Each drum-like CO3@Ag20 cluster is extended by twelve NO3− ions to form the 2D sql lattice of 1, whereas each ball-shaped SO4@Ag22 cluster with a twisted truncated tetrahedral geometry is pillared by four [Ag6(NO3)3] triangular prisms to form the 3D interpenetrated dia network of 2. Notably, 2 is the first interpenetrated 3D MOF constructed from silver clusters. These results demonstrate the dual role of the anions, which not only internally act as anion templates to induce the formation of silver thiolate clusters but also externally extend the cluster units into the rigid networks. The photoluminescent and electrochemical properties of 2 are discussed in detail. [ABSTRACT FROM AUTHOR]

The ability of multiple CF3-substituted arenes to act as acceptors for anions is investigated. The results of quantum-chemical calculations show that a high degree of trifluoromethyl substitution at the aromatic ring results in a positive quadrupole moment. However, depending on the polarizability of the anion and on the substitution at the arene, three different modes of interaction, namely Meisenheimer complex, side-on hydrogen bonding, or anion-π interaction, can occur. Experimentally, the side-on as well as a η2-type π-complex are observed in the crystal, whereas in solution only side-on binding is found. [ABSTRACT FROM AUTHOR]

The charging and controlled oxidative doping of single organometallic ferrocene nanoparticles is reported in aqueous sodium tetrafluoroborate using the nano-impacts method. It is shown that ferrocene nanoparticles of approximately 105 nm diameter are essentially quantitatively oxidatively doped with the uptake of one tetrafluoroborate anion per ferrocene molecule at suitably high overpotentials. By using lower potentials, it is possible to achieve low doping levels of single nanoparticles in a controlled manner. [ABSTRACT FROM AUTHOR]

Reaction of Zn(OAc)2 ⋅2 H2O with 2,6-diisopropylphenyl phosphate (dippH2) in the presence of pyridine-4-carboxaldehyde (Py-4-CHO) in methanol resulted in the isolation of a tetrameric zinc phosphate cluster [Zn(dipp)(Py-4-CH(OH)(OMe))]4 ⋅4 MeOH ( 1) with four hemiacetal moieties stabilized on the double-4-ring inorganic cubane cluster. The change of solvent from methanol to acetonitrile leads to the formation of [Zn(dipp)(Py-4-CHO)]4 ( 2), in which the coordinated Py-4-CHO retains its aldehydic form. Dissolution of 1 in CD3CN readily converts it to the aldehydic form and yields 2. Similarly 2, which exists in the aldehyde form in CD3CN, readily converts to the hemiacetal form in CD3OD/CH3OH. Compound 1 is an unprecedented example in which four hemiacetals have been stabilized on a single molecule in the solid state retaining its stability in solution as revealed by its 1H NMR spectrum in CD3OD. The solution stability of 1 and 2 has further been confirmed by ESI-MS studies. To generalize the stabilization of multiple hemiacetals on a single double-four-ring platform, pyridine-2-carboxaldehyde (Py-2-CHO) was used as the auxiliary ligand in the reaction between zinc acetate and dippH2, leading to isolation of [Zn(dipp)(Py-2-CH(OH)(OMe))]4 ( 3). Understandably, recrystallization of 3 from acetonitrile yields the parent aldehydic form, [Zn(dipp)(Py-2-CHO)]4 ( 4). Single-crystal X-ray diffraction studies reveal that supramolecular bonding, aided by hydrogen-bonding interactions involving the hemiacetal functionalities (C−OH, C−OMe, and C−H), are responsible for the observed stabilization. The hemiacetal/aldehyde groups in 1 and 2 readily react with p-toluidine, 2,6-dimethylaniline, and 4-bromoaniline to yield the corresponding tetra-Schiff base ligands, [Zn(dipp)(L)]4 (L=4-methyl- N-(pyridin-4-ylmethylidene)aniline ( 5), 2,6-dimethyl- N-(pyridin-4-ylmethylene)-aniline ( 6), and 4-bromo- N-(pyridin-4-ylmethylene)aniline ( 7)). Isolation of 5- 7 opens up further possibilities of using 1 and 2 as new supramolecular synthons and ligands. [ABSTRACT FROM AUTHOR]

A convergent and highly stereoselective [4+2] cycloaddition of in situ-generated ortho-Quinone methides ( o-QMs) and azlactone enols has been successfully developed through a triple Brønsted acid catalysis strategy. This protocol provides an efficient and mild access to various densely functionalized dihydrocoumarins bearing adjacent quaternary and tertiary stereogenic centers in high yields with excellent diastereo- and enantioselectivity. [ABSTRACT FROM AUTHOR]

A highly efficient and mild transamidation of amides with amines co-catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α-amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron-derived Lewis acidity rather than an improved Brønsted acidity of acetic acid. [ABSTRACT FROM AUTHOR]

A novel family of dipeptide-based multifunctional quaternary phosphonium salts has been developed as chiral phase-transfer catalysts, which feature ready accessibility and structure modularity, allowing easy fine-tunings of activity. They demonstrated high efficiency in catalyzing the tandem asymmetric Michael addition/intramolecular SN2 reaction between 6 or 7-substituted conjugate enones and malonates, providing synthetically important five or six-membered carbocycles and heterocycles in good yields and with good to excellent enantioselectivities. [ABSTRACT FROM AUTHOR]

The synthesis of small organic molecules as probes for discovering new therapeutic agents has been an important aspect of chemical biology. One of the best ways to access collections of small molecules is to use various techniques in diversity-oriented synthesis (DOS). Recently, a new form of DOS, namely 'relay catalytic branching cascades' (RCBCs), has been introduced, wherein a common type of starting material reacts with several scaffold-building agents (SBAs) to obtain structurally diverse molecular scaffolds under the influence of catalysts. Herein, the RCBC reaction of a common type of substrate with SBAs is reported to give two different types of molecular scaffolds and their formation is essentially dependent on the type of catalyst used. [ABSTRACT FROM AUTHOR]

New and interesting polycyclic compounds have been synthesized from non-conjugated diyne systems by dual gold catalysis. A quaternary carbon center in the backbone and the accompanying Thorpe-Ingold effect enabled the unprecedented insertion of sp3 and sp2 CH bonds that for the first time were incorporated within the backbone of the diyne system and allowed the construction of complex polycyclic carbon scaffolds inaccessible by previous approaches in which the CH bonds for the insertion were situated at the other end of the alkyne. [ABSTRACT FROM AUTHOR]

As a result of detailed mechanistic and kinetic studies, we have proposed that PdX2-catalyzed oxidative coupling of o-alkynylanilines 1 with terminal alkynes 2 under aerobic conditions is initiated by aminopalladation of 1 followed by ligand exchange of the resulting s-indolylpalladium( II) complex with 2, reductive elimination and N-demethylation. Side reactions associated with intermediates on the way to 2,3-disubstituted indoles 3 were identified, and the roles of acetate and iodide in channeling the reaction towards the desired product were established. Based on kinetic and spectroscopic studies, the soluble iodide-ligated Pd0 species was proposed to be the resting state of the catalyst and its oxidation to active PdII species was the turnover-limiting step. Catalytic conditions with low loading of Pd(OAc)2 (0.0005 to 0.001 equiv) were subsequently developed. [ABSTRACT FROM AUTHOR]

Trifluoromethylation of propargylic alcohols to provide (Z)-α-trifluoromethylated enones and β-unsubstituted a-trifluoromethylated enones proceeded with high yield and selectivity in the presence of CuI/Re2O7. The Z isomer was formed under kinetic control, though it is less stable than the E isomer in terms of steric repulsion. [ABSTRACT FROM AUTHOR]

Gold-catalyzed cascade cyclization/1,2-rearrangement of 1-(2-furanyl)phenyl propargyl alcohols has been developed, which provides a rapid and efficient access to multisubstituted 1-naphthols bearing an enal or enone moiety with high stereoselectivity. The (Z)- or (E)- stereochemistry can be easily controlled by choosing protected- or non-protected substrates. The utility of the methodology has been illustrated in the first total synthesis of wailupemycin G. [ABSTRACT FROM AUTHOR]

A straightforward and scalable eight-step synthesis of new N-heterocyclic carbenes (NHCs) has been developed from inexpensive and readily available 2-nitro- m-xylene. This process allows for the preparation of a novel class of NHCs coined ITent ('Tent' for 'tentacular') of which the well-known IMes ( N, N′-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), IPr ( N, N′-bis(2,6-di(2-propyl)phenyl)imidazol-2-ylidene) and IPent ( N, N′-bis(2,6-di(3-pentyl)phenyl)imidazol-2-ylidene) NHCs are the simplest and already known congeners. The synthetic route was successfully used for the preparation of three members of the ITent family: IPent ( N, N′-bis(2,6-di(3-pentyl)phenyl)imidazol-2-ylidene), IHept ( N, N′-bis(2,6-di(4-heptyl)phenyl)imidazol-2-ylidene) and INon ( N, N′-bis(2,6-di(5-nonyl)phenyl)imidazol-2-ylidene). The electronic and steric properties of each NHC were studied through the preparation of both nickel and palladium complexes. Finally the effect of these new ITent ligands in Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig cross-couplings was investigated. [ABSTRACT FROM AUTHOR]

Assimilation of open metal sites (OMSs) and free functional organic sites (FOSs) with a framework strut has opened up a new route for the fabrication of novel metal-organic materials, thereby providing a unique opportunity to explore their multiple functionalities. A new metal-organic framework (MOF), {[Cu(ina)2(H2O)][Cu(ina)2(bipy)]⋅2 H2O} n ( 1) (ina=isonicotinate, bipy=4,4′-bipyridine), has been synthesized and characterized. Complex 1 is crystallized in the orthorhombic noncentrosymmetric space group Aba2 and consists of two different 2D coordination polymers, [Cu(ina)2(H2O)] n and [Cu(ina)2(bipy)] n, with entrapped solvent water molecules. Hydrogen-bonding interactions assemble these two different 2D coordination layers in a single-crystal structure with interdigitation of pendant 4,4′-bipy from one layer into the groove of another. Upon removal of guest molecules, 1 undergoes a structural transformation in single-crystal-to-single-crystal fashion with expansion of the effective void space. Each metal center is five-coordinated and thus can potentially behave as an OMS, and the free pyridyl groups of pendant 4,4′-bipy moieties and free CO groups can act as free FOSs. Thus, owing to presence of both OMSs and free FOSs, the framework exhibits multifunctional properties. Owing to the presence of OMSs, the framework can act as a Lewis acid catalyst as well as a small-molecule sensor material, and in a similar way, owing to the presence of free FOSs, it performs as a Lewis base catalyst and a cation sensor material. Furthermore, owing to noncentrosymmetry with large polarity along a particular direction, it shows strong second-harmonic generation/nonlinear optical (SHG-NLO) activity. [ABSTRACT FROM AUTHOR]

Azoles reacting in tandem: The ortho‐stereodirecting effect is the key to the stereoselective synthesis of (Z)‐N‐alkenylazoles I through the tosylhydrazide‐mediated Pd‐catalyzed cross‐coupling reaction of α‐N‐azoleacetophenones with ortho‐substituted aryl halides and nonaflates (see scheme). Additionally, the preorganization of the alkene allowed for the development of an auto‐tandem reaction involving an intramolecular CH arylation leading to pyrroloisoquinolines II. [ABSTRACT FROM AUTHOR]