Structural data of phenanthrene-9,10-dicarbonitriles.

In this data article, we present the single-crystal XRD data of phenanthrene-9,10-dicarbonitriles. Detailed structure analysis and photophysical properties were discussed in our previous study, "Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies" (Afanasenko et al., 2020).

[2 + 1 + 1] Assembly of spiro β-lactams by Rh(ii)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles.

A domino synthesis of dispiro-fused N-vinyl β-lactams from diazo-Meldrum's acid and 2H-azirines or 5-alkoxyisoxazoles via the "2-azabuta-1,3-diene formation/Staudinger ketene-imine cycloaddition" sequence is described. The Rh2(Piv)4-catalyzed formation of the 2-azabuta-1,3-diene intermediates in the first stage of the reaction sequence proceeds via addition of the rhodium carbenoid to the azirines/isoxazoles and provides the first example of the generation of iminium-type ylides from diazo-Meldrum's acid. This methodology was extended to monospiro-β-lactams, which were synthesized in two steps using acyclic α-diazocarbonyl compounds in the stage of the formation of 2-azabuta-1,3-dienes.

Synthesis and Biological Evaluation of Novel Thymidine Analogs Containing 1-1,2,3-Triazolyl, 1-Tetrazolyl, and 2-Tetrazolyl Fragments.

3'-Azidothymidine (AZT) reacts with 1-propargyl-5-R-1- and 2-propargyl-5-R-2-tetrazoles (R = H, Me, CHCOOEt, CHCON(CH), Ph, 2-CH-CH, or 4-NO-CH) the Cu(I)-catalyzed asymmetric [3 + 2] cycloaddition to give 3'-modified thymidine analogs incorporating 1-1,2,3-triazolyl, 1-, and 2-tetrazolyl fragments in 41-76% yield. The structures of the obtained compounds have been elucidated by means of HRESI-MS, H and C{H} NMR, and single crystal X-ray diffraction {for 3'-[4-(1-5-,-dimethylaminocarbonylmethyltetrazol-1-yl)-1-1,2,3-triazol-1-yl]thymidine }. biological evaluation of the prepared compounds has been performed; they have exhibited low activity against phenotypic HIV-1.

Synthesis of 2-(Di/tri/tetraazolyl)-2 H-azirine-2-carboxylates by Halogen Substitution: Evidence for an S2'-S2' Cascade Mechanism.

An effective and operationally simple method for the preparation of methyl 2-(di/tri/tetraazol-1-yl)-2 H-azirine-2-carboxylates from accessible methyl 2-halo-2 H-azirine-2-carboxylates and NH-azoles has been developed. The azoles having enhanced NH acidity, react with 2-halo-2 H-azirines in the presence of EtN in a deprotonated form, while the azoles having highly nucleophilic sp nitrogen react in neutral form. According to the DFT calculations, the substitution of the halogen by the azole proceeds via an S2'-S2' cascade, with the initial conjugate substitution of the halogen being the rate-determining step.

Rh(II)-Catalyzed Transannulation of 1,2,4-Oxadiazole Derivatives with 1-Sulfonyl-1,2,3-triazoles: Regioselective Synthesis of 5-Sulfonamidoimidazoles.

An effective method for the synthesis of fully substituted 5-sulfonamidoimidazoles by Rh(II)-catalyzed transannulation of 1,2,4-oxadiazole derivatives with N-sulfonyl-1,2,3-triazoles is reported. The reaction works well with both aromatic 1,2,4-oxadiazoles and 1,2,4-oxadiazol-5-ones providing a flexible approach to N-(alkoxy/amino)carbonyl- and N-alkyl-substituted imidazoles. Both the disclosed reactions are completely regioselective and provide the first examples of a carbenoid-mediated transformation of N,N,O-heterocycles.

Metalated Ir(III) Complexes Based on the Luminescent Diimine Ligands: Synthesis and Photophysical Study.

A series of novel diimine (NN) ligands containing developed aromatic [2,1- a]pyrrolo[3,2- c]isoquinoline system have been prepared and used in the synthesis of Ir(III) luminescent complexes. In organic solvents, the ligands display fluorescence which depends strongly on the nature of solvents to give moderate to strong orange emission in aprotic solvents and shows a considerable blue shift and substantial increase in emission intensity in methanol. Insertion of electron-withdrawing and -donating substituents into peripheral phenyl fragment has nearly no effect onto emission parameters.

A rare example of a compact heteroleptic cyclometalated iridium(iii) complex demonstrating well-separated dual emission.

A series of [Ir(C^N)2(NN)][PF6] complexes in which NN is 5-(4-ethynylphenyl)-2,2'-bipyridine has been synthesized and characterized by spectroscopic methods. All novel complexes exhibit unique singlet-triplet dual emission in solution with two well-separated emission bands. The mechanism of dual emission has been elucidated on the basis of experimental data and confirmed by TDDFT calculations.

Composites based on heparin and MIL-101(Fe): the drug releasing depot for anticoagulant therapy and advanced medical nanofabrication.

We describe the synthesis and properties of a new composite material based on heparin and MIL-101(Fe) metal-organic framework. The intrinsic instability of MIL-101(Fe) towards hydrolysis enables binding of heparin molecules to the framework structure as is evidenced by DFT calculations and adsorption experiments. The de novo formed heparin-MOF composites showed good biocompatibility in in vitro and demonstrated pronounced anticoagulant activity.

Halides Held by Bifurcated Chalcogen-Hydrogen Bonds. Effect of μCl Contacts on Dimerization of Cl(carbene)Pd Species.

The reaction of cis-[PdCl(CNCy)] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{ C(N(H)4,5-R-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH)- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeCH (7), 4-FCH (8), 4-ClCH (9), 3,4-FCH (10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μCl and also Pd···Pd metallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization.

Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2 H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of Pyrazole-Nitrogen Heterocycle Dyads.

2-(1 H-Pyrazol-1-ylcarbonyl)-2 H-azirines were synthesized by in situ trapping of 2 H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles, with pyrazoles. According to DFT calculations, the selectivity of nucleophilic substitution at the carbonyl group of 2 H-azirine-2-carbonyl chloride by a pyrazole nucleophile, which is a mixture of two tautomers, is controlled by thermodynamic factors. 2-(1 H-Pyrazol-1-ylcarbonyl)-2 H-azirines are excellent precursors for the preparation of two other pyrazole-nitrogen heterocycle dyads: 5-(1 H-pyrazol-1-yl)oxazoles by photolysis and 1-(1 H-pyrrol-2-ylcarbonyl)-1 H-pyrazoles by a Ni(II)-catalyzed reaction with 1,3-dicarbonyl compounds.

Relative Reactivity of Benzothiophene-Fused Enediynes in the Bergman Cyclization.

To find promising analogues of naturally occurring enediyne antibiotics with a sufficient reactivity in the Bergman cyclization and moderately stable under isolation and storage, a scale of relative enediynes reactivity was created on the basis of calculated free activation energies for the Bergman cyclization within 12 known and new benozothiophene, benzene, and cinnoline annulated 9- and 10-membered enediynes. To verify the predicted reactivity/stability balance, three new carbocyclic enediynes fused to a benzothiophene core bearing 3,4,5-trimethoxybenzene, fluoroisopropyl, and isopropenyl substituents were synthesized using the Nicholas-type macrocyclization. It was confirmed that annulation of a 3,4,5-trimethoxybenzene moiety to a 10-membered enediyne macrocycle imparts high reactivity to an enediyne while also conferring instability under ambient temperature.

Reactions of 1,5-Diaryl-3-(trifluoromethyl)pent-1-en-4-yn-3-yl Cations with Benzene in TfOH. Synthesis of CF-"Helicopter"-Like Molecules.

Trimethylsilyl ethers of 1,5-diaryl-3-(trifluoromethyl)pent-1-en-4-yn-3-oles in superacid CFSOH (TfOH) give rise to the corresponding intermediate CF-pentenynyl cations. These species react with benzene to afford conjugated CF-pentenynes, which undergo subsequent cyclization, first, into CF-cycloheptadienes and, finally, into unusual CF-"helicopter"-like bicyclic structures.

Gold(I) Alkynyls Supported by Mono- and Bidentate NHC Ligands: Luminescence and Isolation of Unprecedented Ionic Complexes.

Reactions of NHC·HX (NHC = 1-benzyl-3-methylbenzimidazol-2-ylidene, X = Br, PF) and (AuC≡CR) (R = Ph, CHOH) in the presence of CsCO initially afford compounds of the general formula [(NHC)Au][(RC)Au]X, which can be isolated by crystallization. With increased reaction time, only the expected mononuclear complexes of the type [NHCAuC≡CR] are produced. The crystal structure of [(NHC)Au][(PhC)Au]PF reveals an unprecedented triple-decker array upheld by a remarkably short (2.

Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines.

An efficient two-step procedure "imine formation/azirine-carbenoid coupling" has been developed for the preparation of 1,2-dihydropyrimidines from azirine-2-carbaldehydes, primary amines, and diazo carbonyl compounds under Rh(II) catalysis. The formation of 1,2-dihydropyrimidines involves 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-2-carbaldimine. According to the DFT calculations the reaction proceeds via dissociation of the metal-bound complex of the azirinium ylide to metal-free azirinium ylide, ring-opening of the latter to give a 1,5-diazahexa-1,3,5-triene, followed by 1,6-cyclization.

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd Complexes.

The reaction of cis-[PdCl(CNXyl)] (Xyl = 2,6-MeCH) with various 1,3-thiazol- and 1,3,4-thiadiazol-2-amines in chloroform gives a mixture of two regioisomeric binuclear diaminocarbene complexes. For 1,3-thiazol-2-amines the isomeric ratio depends on the reaction conditions and kinetically (KRs) or thermodynamically (TRs) controlled regioisomers were obtained at room temperature and on heating, respectively. In CHCl solutions, the isomers are subject to reversible isomerization accompanied by the cleavage of Pd-N and C-N bonds in the carbene fragment XylNCN(R)Xyl.

Aurophilicity in Action: Fine-Tuning the Gold(I)-Gold(I) Distance in the Excited State To Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)-NHC Complexes.

The solution-state emission profiles of a series of dinuclear Au(I) complexes 4-6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1-3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and in the case of 5, which is nonemissive when neat, green luminescence emerges.

Click-Type Pt -Mediated Hydroxyguanidine-Nitrile Coupling Provides Useful Catalysts for Hydrosilylation Cross-Linking.

The nitrile complexes trans-[PtCl (RCN) ] (R=Et (NC1), tBu (NC2), Ph (NC3), p-BrC H (NC4)) and cis-[PtCl (RCN) ] (R=Et (NC5), tBu (NC6), Ph (NC7)) react with 1 equiv of the hydroxyguanidine OC H NC(=NOH)NH (HG) furnishing the mono-addition products trans- and cis-[PtCl (RCN){NH=C(R)ON=C(NH )NC H O}] (1-4 and 9-11; 7 examples; 54-74 % yield). Treatment of any of the nitrile complexes NC1-NC7 with HG in a 1:2 molar ratio generated the bis-addition products trans- and cis-[PtCl {NH=C(R)ON=C(NH )NC H O} ] (5-8 and 12-14; 7 examples; 69-89 % yield). The Pt -mediated coupling between nitrile ligands and HG proceeds substantially faster than the corresponding reactions involving amid- and ketoximes and gives redox stable products under normal conditions.

Cu(I)-NHC-Catalyzed (2 + 3)-Annulation of Tetramic Acids with 2H-Azirines: Stereoselective Synthesis of Functionalized Hexahydropyrrolo[3,4-b]pyrroles.

A stereoselective and high-yield synthesis of hexahydropyrrolo[3,4-b]pyrroles from tetramic acids and 2H-azirines under Cu(I)-NHC catalysis is developed. An unusual N-C2 azirine bond cleavage, initiated by a copper enolate, was rationalized in terms of a free radical reaction mechanism.

Reactions of CF3-enones with arenes under superelectrophilic activation: a pathway to trans-1,3-diaryl-1-CF3-indanes, new cannabinoid receptor ligands.

4-Aryl-1,1,1-trifluorobut-3-en-2-ones ArCH[double bond, length as m-dash]CHCOCF3 (CF3-enones) react with arenes in excess of Brønsted superacids (TfOH, FSO3H) to give, stereoselectively, trans-1,3-diaryl-1-trifluoromethyl indanes in 35-85% yields. The reaction intermediates, the O-protonated ArCH[double bond, length as m-dash]CHC(OH(+))CF3 and the O,C-diprotonated ArHC(+)CH2C(OH(+))CF3 species, have been studied by means of (1)H, (13)C, (19)F NMR, and DFT calculations. Both types of the cations may participate in the reaction, depending on their electrophilicity and electron-donating properties of the arenes.

Ring-Closing Metathesis of Co2(CO)6-Alkyne Complexes for the Synthesis of 11-Membered Dienediynes: Overcoming Thermodynamic Barriers.

The feasibility of ring-closing metathesis (RCM) as a synthetic entry to 10- and 11-membered dienediynes fused to a benzothiophene core was explored by experimental and theoretical investigations. An established sequence of iodocyclization of o-(buta-1,3-diynyl)thioanisoles followed by Sonogashira coupling to form diethynylbenzothiophenes was used to synthesize terminal benzothiophene-fused enediyne diolefins as substrates for RCM. Encountering an unexpected lack of reactivity of these substrates under standard RCM conditions, we applied DFT calculations to reveal that the underlying cause was a positive change in Gibbs free energy.

Azirinium ylides from α-diazoketones and 2H-azirines on the route to 2H-1,4-oxazines: three-membered ring opening vs 1,5-cyclization.

Strained azirinium ylides derived from 2H-azirines and α-diazoketones under Rh(II)-catalysis can undergo either irreversible ring opening across the N-C2 bond to 2-azabuta-1,3-dienes that further cyclize to 2H-1,4-oxazines or reversibly undergo a 1,5-cyclization to dihydroazireno[2,1-b]oxazoles. Dihydroazireno[2,1-b]oxazoles derived from 3-aryl-2H-azirines and 3-diazoacetylacetone or ethyl diazoacetoacetate are able to cycloadd to acetyl(methyl)ketene generated from 3-diazoacetylacetone under Rh(II) catalysis to give 4,6-dioxa-1-azabicyclo[3.2.

Novel (cyanamide)Zn(II) complexes and zinc(ii)-mediated hydration of the cyanamide ligands.

The cyanamides NCNR2 (R2 = Me2, Ph2, C5H10) react with ZnX2 (X = Cl, Br, I) in a 2 : 1 molar ratio at RT, giving a family of zinc(ii) complexes [ZnX2(NCNR2)2] (R2 = Me2, X = Cl , X = Br , X = I ; R2 = C5H10, X = Cl , X = Br ; X = I ; R2 = Ph2, X = Cl , X = Br , X = I ; 75-92% yields). Complexes and undergo ligand redistribution in wet CH2Cl2 solutions giving the [Zn(NCNPh2)4(H2O)2][Zn2(μ-X)2X4] (X = Cl , Br ) species that were characterized by (1)H NMR, HRESI-MS, and X-ray diffraction. Halide abstraction from by the action of AgCF3SO3 or treatment of Zn(CF3SO3)2 with NCNR2 (R2 = Me2, C5H10) leads to labile complexes [Zn(CF3SO3)2(NCNR2)3] (R2 = Me2, ; C5H10, ).

Zinc(II)-mediated nitrile-amidoxime coupling gives new insights into H⁺-assisted generation of 1,2,4-oxadiazoles.

The cyanamides Me2NCN (1a), OC4H8NCN (1b), and PhC(═O)N(H)CN (1c) and the conventional nitriles PhCN (1d) and EtCN (1e) react with 1 equiv of each of the amidoximes R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) in the presence of 1 equiv of ZnCl2 producing the complexes [ZnCl2{HN═C(R)ON═C(R')NH2}] (R/R' = NMe2/Me (3a), NMe2/Ph (3b), NC4H8O/Me (3c), NC4H8O/Ph (3d), N(H)C(═O)Ph/Me (3e), N(H)C(═O)Ph/Ph (3f), Ph/Me (3g), Ph/Ph (3h), Et/Ph (3j)) with the chelate ligands originating from the previously unreported zinc(II)-mediated nitrile-amidoxime coupling. Addition of 1 equiv of p-TolSO3H to any of one 3a-h, 3j results in the ligand liberation and formation of the iminium salts [H2N═C(R)ON═C(R')NH2](p-TolSO3) ([4a-j](p-TolSO3)), which then at 20-65 °C spontaneously transform to 1,2,4-oxadiazoles (5a-j). As a side reaction, cyanamide derived species [4a-f](p-TolSO3) undergo Tiemann rearrangement to produce the substituted ureas R'NHC(═O)NH2 (R' = Me (6a), Ph (6b)) and RC(═O)NH2 (R = NMe2 (6c), NC4H8O (6d), N(H)C(═O)Ph (6e)), whereas phenyl and ethyl cyanide derivatives besides their transformation to the oxadiazoles undergo hydrolysis to the parent amidoxime R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) and the carboxamides RC(═O)NH2 (R = Ph (6f), Et (6g)).

Dichloridobis[3-(4-meth-oxy-phen-yl)-2-methyl-5-(piperidin-1-yl)-2,3-di-hydro-1,2,4-oxa-diazole-κN (4)]platinum(II).

In title compound, [PtCl2(C15H21N3O2)2], the Pt(II) cation, located on an inversion center, is coordinated by two Cl(-) anions and two 3-(4-meth-oxy-phen-yl)-2-methyl-5-(piperidin-1-yl)-2,3-di-hydro-1,2,4-oxa-diazole ligands in a distorted Cl2N2 square-planar geometry. The di-hydro-oxa-diazole and piperidine rings display envelope (with the non-coordinating N atom as the flap atom) and chair conformations, respectively. In the crystal, weak C-H⋯Cl hydrogen bonds link the mol-ecules into supra-molecular chains running along the b axis.