Effective Dual-Functional Metal-Organic Framework (DF-MOF) as a Catalyst for the Solvent-Free Cycloaddition Reaction.

A new porous metal-organic framework, [Co (oba) (bpdh)]·(DMF) (TMU-63), containing accessible nitrogen-rich diazahexadiene groups was successfully prepared with the solvothermal assembly of 5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), 4,4'-oxybis(benzoic) acid (oba), and Co(II) ions. The combination of Lewis basic functional groups and porosity leads to high performance in CO2 adsorption and conversion in the cycloaddition reaction of epoxides under solvent-free conditions. To further enhance the catalytic efficiency of TMU-63, we introduced a highly acidic malonamide ligand into the structure via solvent-assisted ligand exchange (SALE) as a postsynthesis method. Incorporating different percentages of N1,N3-di(pyridine-4-yl) malonamide linker (4-dpm) into TMU-63 created a new porous structure. Powder X-ray diffraction (PXRD) and NMR spectroscopy confirmed that 4-bpdh was successfully replaced with 4-dpm in the daughter MOF, TMU-63S. The catalytic activity of both MOFs was confirmed by significant amounts of CO2 cycloaddition of epoxides under solvent-free conditions. The catalytic cycloaddition activities were found to be well-correlated with the Lewis base/Brønsted acid distributions of the materials examined in the TMU-63S series, showing that the concurrent presence of both acid and base sites was desirable for high catalytic activity. Furthermore, the heterogeneous catalysts could easily be separated out from the reaction mixtures and reused four times without loss of catalytic activity and with no structural deterioration.

Strategic design and synthesis of star-shaped organic linkers for mesoporous MOFs.

In the process of designing new MOFs with the aim of having a specific morphology, the shape of the linkers and the choice of coordinating metals have major importance. In this study, the aim to create novel hnb non-interpenetrating MOFs led us to choose tritopic linkers. Novel star-shaped molecules, presenting trigonal geometry and based on aromatic rings, were synthesized. For more convenient synthesis of the library, C-C coupling reactions via a direct arylation methodology were performed. This new synthetic tool, together with the idea of a molecule as a modular combination of smaller building blocks, made possible the fast, cheap and reproducible production of this class of compounds and also its scale-up. With one of the compounds, a MOF was synthesized and characterised via its specific surface area, which varies between 1681 and 3770 m2 g-1.

Catalytic Asymmetric Synthesis of Diketopiperazines by Intramolecular Tsuji-Trost Allylation.

We report the intramolecular Tsuji-Trost reaction of Ugi adducts to give spiro-diketopiperazines in high yield and with high enantioselectivity. This approach allows the catalytic asymmetric construction of a broad range of these medicinally important heterocycles under mild conditions, in two steps from cheap, commercially available starting materials.

Synthesis of highly functionalized 1,6-dihydropyridines via the Zn(OTf)2-catalyzed three-component cascade reaction of aldimines and two alkynes (IA2-coupling).

A zinc(ii) triflate catalyzed three component synthesis of 1,6-dihydropyridines, involving aldimines, alkynes and electron-deficient dimethyl acetylenedicarboxylate (DMAD), in good to excellent yields has been described. Besides a range of different N-substituents, a variety of both aromatic and aliphatic alkynes could be used. The application of electron-deficient propiolates instead of DMAD resulted in regiospecific incorporation of the ester functionality on the 1,6-dihydropyridine ring. The reaction proceeds via a cascade reaction involving nucleophilic addition of the metal acetylide to the imine, followed by the addition of the intermediately formed propargylic amine to the electron-deficient alkyne and subsequent 6-endo dig cyclization.

Iodospirocyclization of Tryptamine-Derived Isocyanides: Formal Total Synthesis of Aspidofractinine.

The N-iodosuccinimide-mediated spirocyclization of tryptamine-derived isocyanides to generate spiroindolenines is reported. The products contain both an imine and an imidoyl iodide as flexible handles for follow-up chemistry. Nucleophilic addition typically occurs chemoselectively on the imine moiety with complete diastereoselectivity, providing opportunities for the construction of complex molecular frameworks. The synthetic potential of the method was showcased in the formal total synthesis of (±)-aspidofractinine.

Stereoselective Synthesis of Functionalized Bicyclic Scaffolds by Passerini 3-Center-2-Component Reactions of Cyclic Ketoacids.

We report the use of bifunctional starting materials (ketoacids) in a diastereoselective Passerini three-center-two-component reaction. Study of the reaction scope revealed the required structural features for stereoselectivity in the isocyanide addition. In this system, an interesting isomerization of the primary Passerini product - the α-carboxamido lactone - into an atypical product, an α-hydroxy imide, was found to occur under acidic conditions. Furthermore, enantioenriched Passerini products can be generated from an enantioenriched ketoacid obtained by chemoenzymatic synthesis.

Thiazine-2-thiones as Masked 1-Azadienes in Cascade Dimerization Reactions).

We report the unexpected formation of a 1-azadiene dimer from 4,6-diphenyl-3,6-dihydro-2H-1,3-thiazine-2-thiones under prolonged microwave irradiation. In this manner, thiazine-2-thiones act as "masked" 1-azadiene equivalents, which makes them useful synthetic tools to access complex heterocyclic frameworks. We compare this dimerization with earlier approaches and elaborate on the observed diastereoselectivity.

Removal of the pyridine directing group from α-substituted N-(pyridin-2-yl)piperidines obtained via directed Ru-catalyzed sp3 C-H functionalization.

Two strategies, "hydrogenation-hydride reduction" and "quaternization-hydride reduction", are reported that make use of mild reaction conditions (room temperature) to efficiently remove the N-pyridin-2-yl directing group from a diverse set of C-2-substituted piperidines that were synthesized through directed Ru-catalyzed sp(3) C-H functionalization. The deprotected products are obtained in moderate to good overall yields irrespective of the strategy followed, indicating that both methods are generally equally effective. Only in the case of 2,6-disubstituted piperidines, could the "quaternization-hydride reduction" strategy not be used. The "hydrogenation-hydride reduction" protocol was successfully applied to trans- and cis-2-methyl-N-(pyridin-2-yl)-6-undecylpiperidine in a short synthetic route toward (±)-solenopsin A (trans diastereoisomer) and (±)-isosolenopsin A (cis diastereoisomer). The absolute configuration of the enantiomers of these fire ant alkaloids could be determined via VCD spectroscopy.

A Cobalt Mediated Nitrene Transfer aza-Wittig Cascade Reaction To Access 1,3,4-Oxadiazole Scaffolds.

A cobalt(II) mediated three-component synthesis of 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imines using sulfonyl azides, N-isocyaniminotriphenylphosphorane (NIITP), and carboxylic acids has been developed. This one-pot tandem reaction starts with a nitrene transfer to NIITP, followed by addition of the carboxylic acid to the in situ formed carbodiimide and subsequent intramolecular aza-Wittig reaction. Both the steric constraints of carboxylic acid and the stoichiometry of the employed cobalt salt determine the selectivity toward the two products, i.e. 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imine versus 5-substituted-4-tosyl-2,4-dihydro-3H-1,2,4-triazol-3-one.

Dynamic disorder in the crystal structure of an organic semiconductor: an unusual phase transition involving the heat capacity.

(E,E)-1-[2-(4-Nitrophenyl)ethenyl]-4-[2-(2,4-dimethoxyphenyl)ethenyl]benzene was characterised by X-ray diffraction and shown to be dynamically disordered at room temperature. The structure was re-determined over a range of temperatures to infer the thermodynamic parameters related to this disorder. A phase transition of third order according to the Ehrenfest classification scheme was discovered. To the best of our knowledge, this is the first experimentally observed phase transition of formal third order. It can be explained by the involvement of long-range lattice vibrations.

Novel diarylpyridinones, diarylpyridazinones and diarylphthalazinones as potential HIV-1 nonnucleoside reverse transcriptase inhibitors (NNRTIs).

In this Letter, we report on diarylpyridinone, diarylpyridazinone and diarylphthalazinone analogs as potential inhibitors of HIV-1 nonnucleoside reverse transcriptase (NNRTIs). The most promising compounds in these series are three diarylpyridazinones 25a, 25l and 25n which demonstrated submicromolar activity against wild-type HIV-1 and moderate activity against the single mutant strain Ba-L V106A.

Synthesis of Carbazoles by a Diverted Bischler-Napieralski Cascade Reaction.

An unforeseen twist in a seemingly trivial Bischler-Napieralski reaction led to the selective formation of an unexpected carbazole product. The reaction proved to be general, providing access to a range of diversely substituted carbazoles from readily available substrates. Judicious variation of substituents revealed a complex cascade mechanism comprising no less than 10 elementary steps, that could be diverted in multiple ways toward various other carbazole derivatives.

Symmetrical and nonsymmetrical chromophores with Tröger's base skeleton: chiroptical, linear, and quadratic nonlinear optical properties--a joint theoretical and experimental study.

We report on the novel chiral push-pull chromophores derived from 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine (Tröger's base skeleton). The synthesis of symmetrical chromophores featuring two identical acceptors, as well as the synthesis of unsymmetrical chromophores featuring only one acceptor is given. Symmetrical chromophores were prepared in the enantiomerically pure form and their chiroptical properties were investigated. Second-order nonlinear optical (NLO) properties of new chromophores were investigated with the aid of hyper-Rayleigh scattering (HRS). The detailed theoretical analysis of the second-order NLO properties of the chromophores was also undertaken. The joint theoretical and experimental studies of chromophores derived from Tröger's base skeleton, in comparison with benchmark chromophores featuring a dimethylamino group as the donor, provided insight into the relationship between the structure of the new chromophores and their NLO properties.

Synthesis and supramolecular organization of regioregular polythiophene block oligomers.

The self-assembly of functional polythiophenes was studied by a bottom-up approach "from molecule to polymer". The synthesis and the X-ray structure of 2,5-dibromo-3-styryl and 3-2',3',4',5',6'-pentafluorostyryl-thiophenes revealed a supramolecular arrangement controlled by pi-pi interactions between the aromatic rings. A [2 + 2] photocyclization reaction in the solid state of (E)-1-2',5'-dibromo-3'-thienyl-2-pentafluorophenylethene triggers the formation of a rare cycloadduct comprising thiophene rings. The X-ray analysis confirmed its rctt stereochemistry. The synthesis of P3HT-b-P3ST and P3HT-b-P3STF block oligomers was achieved by a GRIM method in good yields. An indirect proof of well-defined nanostructured organization was provided by the partial photocyclization of pendant styryl moieties under UV irradiation.

Structures of alkyl-substituted Tröger's base derivatives illustrate the importance of Z' for packing in the absence of strong crystal synthons.

Crystal structures of Tröger's base (5,11-methano-2,8-dimethyl-5,6,11,12-tetrahydrodibenzo[b,f][1,5]diazocine) analogues with the methyl groups replaced by ethyl, iso-propyl and tert-butyl groups were studied. The incidence of Z' > 1 structures increases to rather conspicuous levels. The reasons behind this trend are expanded upon, and a possible explanation is given in the flexibility of the alkyl substituents and van der Waals stabilization. In combination these effects allow for an additional stabilization of the packing by small changes in the molecular conformations, thus expanding the size of the asymmetric unit.

3-(2-Formyl-phen-oxy)propanoic acid.

In the structure of the title compound, C(10)H(10)O(4), the carboxyl group forms a catemer motif in the [100] direction instead of the expected dimeric structures. The carboxylic acid group is found in the syn conformation and the three-dimensional organization in the crystal is based on C-H⋯O and O-H⋯O interactions.

2-(4-Formyl-2,6-dimeth-oxy-phenoxy)-acetic acid.

In the title compound, C(11)H(12)O(6), the aldehyde group is disordered over two sites in a 0.79:0.21 ratio. The carb-oxy-lic acid chain is found in the [ap,ap] conformation due to two intramolecular O-H⋯O hydrogen bonds.

(E)-3-(2,3,4,5,6-Penta-fluoro-styr-yl)thio-phene.

The reaction of thio-phene-3-carboxaldehyde and perfluoro-benzyl-triphenyl-phospho-nium bromide in the presence of sodium hydride gave the title compound, C(12)H(5)F(5)S, in 70% yield. The thiophene and perfluorophenyl groups form a dihedral angle of 5.4 (2)°. The structure is characterized by a head-to-tail organization in a columnar arrangement due to π-π inter-actions between the thio-phene and penta-fluoro-phenyl rings with centroid-centroid distances in the range 3.698 (2)-3.802 (2) Å.

Synthesis of functionalized pyridazin-3(2H)-ones via bromine-magnesium exchange on bromopyridazin-3(2H)-ones.

The potential of halogen-magnesium exchange reactions, followed by quenching with electrophiles, for the functionalization of the pyridazin-3(2H)-one core was investigated. 2-Benzyl-4-bromo-5-methoxy- (1), 2-benzyl-5-bromo-4-methoxy- (4), and 2-benzyl-4,5-dibromopyridazin-3(2H)-one (10) were selected as readily available model substrates. While 1 and 10 gave exclusively C-4 metalation, a tandem reaction involving nucleophilic substitution via addition elimination and bromine-magnesium exchange was observed with 4.