Advances and Challenges in Development of Transition Metal Catalysts for Heterogeneous Hydrogenation of Organic Compounds.

Actual problems of development of catalysts for hydrogenation of heterocyclic compounds by hydrogen are summarized and discussed. The scope of review covers composites of nanoparticles of platinum group metals and 3d metals for heterogeneous catalytic processes. Such problems include increase of catalyst activity, which is important for reduction of precious metals content; development of new catalytic systems which do not contain metals of platinum group or contain cheaper analogues of Pd; control of factors which make influence on the selectivity of the catalysts; achievement of high reproducibility of the catalyst's performance and quality control of the catalysts.

Catalytic Oxidation of Benzoins by Hydrogen Peroxide on Nanosized HKUST-1: Influence of Substituents on the Reaction Rates and DFT Modeling of the Reaction Path.

In this research, the oxidation of a series of benzoins, R-C(=O)-CH(OH)-R, where R = phenyl, 4-methoxyphenyl, 4-bromophenyl, and 2-naphthyl, by hydrogen peroxide in the presence of nanostructured HKUST-1 (suspension in acetonitrile/water mixture) was studied. The respective benzoic acids were the only products of the reactions. The initial average reaction rates were experimentally determined at different concentrations of benzoin, HO and an effective concentration of HKUST-1.

A Close-up Look at the Chemical Space of Commercially Available Building Blocks for Medicinal Chemistry.

The ability to efficiently synthesize desired compounds can be a limiting factor for chemical space exploration in drug discovery. This ability is conditioned not only by the existence of well-studied synthetic protocols but also by the availability of corresponding reagents, so-called building blocks (BBs). In this work, we present a detailed analysis of the chemical space of 400 000 purchasable BBs.

Reductive Recyclization of sp-Enriched Functionalized Isoxazolines into α-Hydroxy Lactams.

An efficient synthesis (up to a 200 g scale) of 3-hydroxypyrrolidin-2-ones bearing alkyl substituents or functional groups at the C-5 position is described. The reaction sequence started from 1,3-dipolar cycloaddition of generated nitrile oxides with (meth-)acrylates into 3-substituted isoxazoline-5-carboxylates. The catalytic hydrogenolysis of the isoxazoline N-O bond was optimal upon using H (1 atm) at rt, with the following order of the catalyst activity: Pd-C > Pd(OH)-C > Pt-C.

Third Generation Buchwald Precatalysts with XPhos and RuPhos: Multigram Scale Synthesis, Solvent-Dependent Isomerization of XPhos Pd G3 and Quality Control by H- and P-NMR Spectroscopy.

The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, OMs = CHSO). The H- and P-NMR spectra of the title complexes and some impurities, measured by various 1D and 2D techniques, were analyzed in detail. The solvent-dependent isomerization of Pd(ABP)(XPhos)(OMs) was studied by NMR, and the X-ray structures of two isomers were determined.

Versatile Reactivity of Mn Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

Reaction of 2,2'-bipyridine (2,2'-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)(EtOH)] led to the formation of binuclear complexes [Mn(Piv)L] (L = 2,2'-bipy (), phen (); Piv is the anion of pivalic acid). Oxidation of or by air oxygen resulted in the formation of tetranuclear Mn complexes [MnO(Piv)L] (L = 2,2'-bipy (), phen ()). The hexanuclear complex [Mn(OH)(Piv)(pym)] () was formed in the reaction of [Mn(Piv)(EtOH)] with pyrimidine (pym), while oxidation of produced the coordination polymer [MnO(Piv)(pym)] ().

Combination of single-molecule magnet behaviour and luminescence properties in a new series of lanthanide complexes with tris(pyrazolyl)borate and oligo(β-diketonate) ligands.

A series of tris(pyrazolyl)borate mono-, di- and trinuclear complexes, [TpLn]X (Ln = Eu, Tb, Gd, Dy, X = various mono-, bis- and tris(β-diketonates) has been prepared. The Tb and Dy complexes are luminescent single molecular magnets (SMM) and exhibit luminescence quantum efficiencies up to 73% for the Tb and 4.4% for the Dy compounds.

Regioselective Synthesis of Functionalized 3- or 5-Fluoroalkyl Isoxazoles and Pyrazoles from Fluoroalkyl Ynones and Binucleophiles.

A facile synthetic route toward either 3- or 5-fluoroalkyl-substituted isoxazoles or pyrazoles containing an additional functionalization site was developed and applied on a multigram scale. The elaborated approach extends the scope of fluoroalkyl substituents for introduction into the heterocyclic moiety, and uses convenient transformations of the side chain for incorporation of fluoroalkyl-substituted azoles into the structures of biologically active molecules. The utility of the obtained building blocks for isosteric replacement of alkyl-substituted isoxazole and pyrazole was shown by the synthesis of fluorinated Isocarboxazid and Mepiprazole analogues.

Synthesis of 5-(Fluoroalkyl)isoxazole Building Blocks by Regioselective Reactions of Functionalized Halogenoximes.

A comprehensive study on the synthesis of 5-fluoroalkyl-substituted isoxazoles starting from functionalized halogenoximes is reported. One-pot metal-free [3 + 2] cycloaddition of CF-substituted alkenes and halogenoximes bearing ester, bromo, chloromethyl, and protected amino groups was developed for the preparation of 5-trifluoromethylisoxazoles. The target 3,5-disubstituted derivatives were obtained in a regioselective manner in good to excellent yield on up to 130 g scale.

Absorption- and Excitation-Modulated Luminescence of Pr, Nd, and Lu Compounds with Dianions of Tetrafluoroterephthalic and Camphoric Acids.

The luminescence of coordination polymers of Pr, Nd, and Lu with tetrafluoroterephthalate and camphorate, [Ln(Fbdc)(DMF)(HO)] (Ln = Pr, Nd, Lu) and [Ln(Camph)(NO)(MeOH)] (Ln = Pr, Nd, Lu), was studied. Ligand-centered and/or metal-centered emissions appear, which depend on the excitation wavelength, ultimately allowing the emitted light color to be adjusted. Low-efficiency ligand-to-metal energy transfer leads to a difference between the excitation spectra of the tetrafluoroterephthalate- and camphorate-Pr compounds, arising from a primary filtering effect on the ligand-centered excitation, by Pr absorption.

Co Complexes with a Tripyridine Ligand, Containing a 2,6-Di--butylphenolic Fragment: Synthesis, Structure, and Formation of Stable Radicals.

Interaction of a tripyridine ligand bearing a 2,6-di--butylphenolic fragment (L, 2,6-di--butyl-4-(3,5-bis(4-pyridyl)pyridyl)phenol) with Co pivalate or chloride led to the formation of one-dimensional coordination polymers [Co(L)Cl] ·EtOH () and [Co(L)(OH)(Piv)] () or a trinuclear complex Co(HO)(L)Cl () (Piv = pivalate). Chemical oxidation of L and - by PbO or K[Fe(CN)], as well as exposure of L (in solution or solid state) and (in solid state) to UV irradiation, led to the formation of free radicals with = 2.0024, which probably originated because of oxidation of 2,6-di--butylphenolic groups.

Regioselective synthesis of isoxazole and 1,2,4-oxadiazole-derived phosphonates via [3 + 2] cycloaddition.

The results of the study on reactions of halogenoximes bearing (protected) functional groups or fluorinated substituents with various phosphorus-containing dipolarophiles are described. To control the regioselectivity of the reaction, vinylphosphonates bearing a leaving group (i.e.

Synthesis of Spirocyclic Pyrrolidines: Advanced Building Blocks for Drug Discovery.

In the context of drug discovery, novel spirocyclic pyrrolidines have been synthesized in two steps from common three- to seven-membered-ring (hetero)alicyclic ketones. The key transformation is a reaction between an electron-deficient exocyclic alkene and an in situ generated N-benzyl azomethine ylide. The developed method has been used to synthesize the central diamine core of the known antibacterial agents Sitafloxacin and Olamufloxacin.

Crystal structures and intense luminescence of tris(3-(2'-pyridyl)-pyrazolyl)borate Tb and Eu complexes with carboxylate co-ligands.

A series of brightly luminescent new mononuclear TpLn(An)(HO) (where An = carboxylate anion, Ln = Eu or Tb and Tp = tris(3-(2'-pyridyl)pyrazolyl)borate) and dinuclear (TpLn)pma(MeOH) (Ln = Eu, Tb, pma = tetraanion of pyromellitic acid) complexes were prepared and characterized by X-ray crystallography. Within each series the compounds possess similar molecular structures, which differ only by the nature of the carboxylate anions. The quantum efficiencies for metal-centered emission of the complexes were up to 29(3)% for Eu and 53(5)% for the Tb compounds and significantly depend on the electronic structure of the additional ligand (i.

Heterometallic Coordination Polymers Assembled from Trigonal Trinuclear Fe2Ni-Pivalate Blocks and Polypyridine Spacers: Topological Diversity, Sorption, and Catalytic Properties.

Linkage of the trigonal complex [Fe2NiO(Piv)6] (where Piv(-) = pivalate) by a series of polypyridine ligands, namely, tris(4-pyridyl)triazine (L(2)), 2,6-bis(3-pyridyl)-4-(4-pyridyl)pyridine (L(3)), N-(bis-2,2-(4-pyridyloxymethyl)-3-(4-pyridyloxy)propyl))pyridone-4 (L(4)), and 4-(N,N-diethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine (L(5)) resulted in the formation of novel coordination polymers [Fe2NiO(Piv)6(L(2))]n (2), [Fe2NiO(Piv)6(L(3))]n (3), [Fe2NiO(Piv)6(L(4))]n·nHPiv (4), and [{Fe2NiO(Piv)6}4{L(5)}6]n·3nDEF (5, where DEF is N,N-diethylformamide), which were crystallographically characterized. The topological analysis of 3, 4, and 5 disclosed the 3,3,4,4-connected 2D (3, 4) or 3,4,4-connected 1D (5) underlying networks which, upon further simplification, gave rise to the uninodal 3-connected nets with the respective fes (3, 4) or SP 1-periodic net (4,4)(0,2) (5) topologies, driven by the cluster [Fe2Ni(μ3-O)(μ-Piv)6] nodes and the polypyridine μ3-L(3,4) or μ2-L(5) blocks. The obtained topologies were compared with those identified in other closely related derivatives [Fe2NiO(Piv)6(L(1))]n (1) and {Fe2NiO(Piv)6}8{L(6)}12 (6), where L(1) and L(6) are tris(4-pyridyl)pyridine and 4-(N,N-dimethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine, respectively.

Phenyl-1-Pyridin-2yl-ethanone-based iron chelators increase IκB-α expression, modulate CDK2 and CDK9 activities, and inhibit HIV-1 transcription.

HIV-1 transcription is activated by the Tat protein, which recruits CDK9/cyclin T1 to the HIV-1 promoter. CDK9 is phosphorylated by CDK2, which facilitates formation of the high-molecular-weight positive transcription elongation factor b (P-TEFb) complex. We previously showed that chelation of intracellular iron inhibits CDK2 and CDK9 activities and suppresses HIV-1 transcription, but the mechanism of the inhibition was not understood.

Porous 2D coordination polymeric formate built up by Mn(II) linking of Fe3O units: influence of guest molecules on magnetic properties.

A first representative of coordination polymers, built from polynuclear carboxylate bridged by mononuclear carboxylate, has been synthesised and structurally characterized. The compound [{Fe(3)O(HCOO)(6)}{Mn(HCOO)(3)(H(2)O)(3)}].3.

Synthesis of quinolines from 3-formylchromone.

A facile and versatile procedure for the synthesis of 3-(2-hydroxybenzoyl)quinolines and 7H-chromeno[3,2-c]quinolin-7-ones was elaborated on the basis of TMSCl-mediated recyclization of 3-formylchromone with various anilines. Limitations and scope of this methodology were established, and a possible mechanism for the heterocyclizations was proposed.

Delicate crystal structure changes govern the magnetic properties of 1D coordination polymers based on 3d metal carboxylates.

Homo- and heterometallic 1D coordination polymers of transition metals (Co II, Mn II, Zn II) have been synthesized by an in-situ ligand generation route. Carboxylato-based complexes [Co(PhCOO)2]n (1 a, 1 b), [Co(p-MePhCOO)2]n (2), [ZnMn(PhCOO)4]n (3), and [CoZn(PhCOO)4]n (4) (PhCOOH=benzoic acid, p-MePhCOOH=p-methylbenzoic acid) have been characterized by chemical analysis, single-crystal X-ray diffraction, and magnetization measurements. The new complexes 2 and 3 crystallize in orthorhombic space groups Pnab and Pcab respectively.

First trinuclear paramagnetic transition metal complexes with redox active ligands derived from TTF: Co2M(PhCOO)6(TTF-CH=CH-py)2.2CH3CN, M = CoII, MnII.

The first paramagnetic homo- and hetero-metallic trinuclear complexes with redox active ligands derived from TTF are synthesized, the central metal ion has an octahedral coordination sphere while the outer Co(II) ions are in a distorted bipyramidal surrounding, bearing TTF-ligands, the magnetic properties show antiferromagnetic coupling leading to a magnetic ground state.

Co(II)-Co(II) paddlewheel complex with a redox-active ligand derived from TTF.

A new trimethyltetrathiafulvalene (Me3TTF) derivative Me3TTF-CH=CH-py bearing a pyridyl was synthesized and coordinated to a cobalt(II) benzoate dimer, having paddlewheel core structure, leading to a complex formulated as Co2(PhCOO)4(Me3TTF-CH=CH-py)2. Single-crystal X-ray diffraction studies of the complex performed at 293 and 100 K evidenced the existence of a weak metal-metal interaction. Magnetic studies revealed an antiferromagnetic behavior, which is explained as the result of the direct exchange between metal centers.

In situ generation of carboxylate: an efficient strategy for a one-pot synthesis of homo- and heterometallic polynuclear complexes.

An efficient strategy for synthesis of a wide range of homo- and heterometallic polynuclear complexes is proposed. The synthesis protocol consists of a two-step one-pot reaction. The first step is the in situ generation of carboxylate anions via oxidation of aromatic aldehydes by metal nitrates in air.

Synthesis, structure, and magnetism of heterometallic carboxylate complexes [MnIII2M(II)4O2(PhCOO)10(DMF)4], M = Mn(II), Co(II), Ni(II).

Three new homo- and heterometallic hexanuclear complexes [Mn(2)M(II)(4)O(2)(PhCOO)(10)(DMF)(4)] (with M = Mn (1), Co (2) or Ni (3) and DMF = dimethylformamide) have been synthesized by redox generation of benzoate ligands from benzaldehyde in a one-pot reaction. All of the compounds are isostructural and crystallize in the I-42d space group of the tetragonal system, data for 1: a = 27.2249(8) Angstroms, c = 25.

[Biomimetic oxidation of benzene by a polynuclear manganese complex [Mn12O12(CH3CO2)16(H2O)4] under mild conditions].

The possibility of monooxygenase enzymes biomimetic construction models with the use of polynuclear manganese complexes was shown. It was demonstration that benzene is oxidized by polynuclear manganese complex [Mn12O12(CH3CO2)16(H2O)4] in acetonitrile solution at room temperature and atmospheric pressure yielding phenol with the selectivity more than 80%. It was determined that the addition of air oxygen as the reoxidizer to the reaction mixture didn't transfer the reaction into the catalytic mode.