Center for Magnetic Resonance

A. P. Molchanov,T. Q. Tran, A. V. Stepakov, G. L. Starova, R. R. Kostikov

«Regioselective cycloaddition of C-carbamoylnitrones to methyl (E)-2-(2-phenylcyclopropylidene)acetate and methyl (E)-2-methylidene-3-phenylcyclopropane-1-carboxylate»

Russ. J. Org. Chem., 2014, 50, 78-82 (russ. 84-88)

DOI: 10.1134/S1070428014010151

N-Aryl-C-(arylcarbamoyl)nitrones regioselectively add to methyl 2-(2-phenylcyclopropylidene)-acetate and methyl 2-methylidene-3-phenylcyclopropanecarboxylate to give in each case two diastereoisomeric 5-oxa-6-azaspiro[2.4]heptane-4-carboxylates.

A.E. Kulyashova, E.V. Mikheeva, N.A. Danilkina, I.A. Balova
“Synthesis of 2-(buta-1,3-diynyl)-N,N-dimethylanilines using reductive methylation step”

Mendeleev Commun., 2014, 24, 102-104

DOI: 10.1016/j.mencom.2014.03.013

Synthesis of 2-(buta-1,3-diynyl)-N,N-dimethylanilines based on reductive methylation of ortho-iodoanilines using CH2O–NaBH3CN and coupling with terminal diacetylens was developed. Altered sequence including dimethylation of 2-(buta-1,3-diynyl)anilines was also successfully achieved and gave higher overall yields in the case of anilines without acceptor substituent in the ring.

A. Penkova, G. Polotskaya, A. Toikka
“Pervaporation composite membranes for ethyl acetate production”
Chem. Eng. Process., 2014, accepted
DOI: 10.1016/j.cep.2014.11.015

T. Minh Dau, Y.-A. Chen, A.J. Karttunen, E.V. Grachova, S.P. Tunik, K.-T. Lin, W.-Y. Hung, P.-T. Chou, T.A. Pakkanen, I.O. Koshevoy
“Tetragold(I) complexes: solution isomerization and tunable solid-state luminescence”
Inorg. Chem., 2014, accepted

A.I. Solomatina, D.V. Krupenya, V.V. Gurzhiy, I. Zlatkin, A.P. Pushkarev, M.N. Bochkarev, N.A. Besley, E. Bichoutskaia, S.P. Tunik
“Cyclometallated platinum(II) complexes containing NHC ligands; synthesis, characterization, photophysics and their application as emitters in OLEDs”
Dalton Trans., 2014, accepted

First paper of 2015 with acknowledgments to CMR:

M.Ya. Demakova, D.S. Bolotin, N.A. Bokach, G.L. Starova, V.Yu. Kukushkin

“Metal-mediated cyanamide–hydroxyguanidine coupling” Inorg Chim. Acta, 2015, 425, 114-117

DOI: 10.1016/j.ica.2014.10.015

Reaction of the cyanamides R₂NCN (R = Me 2a, Et 2b) with the hydroxyguanidine OC₄H₈NC(=NOH)NH₂ (1) in the presence of zinc halides leads to [ZnX₂{HN=C(NR₂)ON=C(NH₂)NC₄H₈O}] derived from the ZnIImediated cyanamide–hydroxyguanidine coupling. This reaction is the first observation of interplay between any nitrile group and any hydroxyguanidine both in metal-involving and metal-free chemistry. Complexes 3a,b–5a,b rather rapidly degrade in solutions at RT, but solvates 3a,b MeOH and 4a MeOH are sufficiently stable in the solid state and they were characterized by IR, HRESI⁺-MS, solid state CP-MAS TOSS ¹³C NMR, and X-ray crystallography (for 3a,b). Complexes 4b and 5a,b were identified in solutions by HRESI⁺-MS.

A.S. Konev, A.F. Khlebnikov, P.I. Prolubnikov, A.S. Mereshchenko, A.V. Povolotskiy, O.V. Levin, A. Hirsch, “Synthesis of New Porphyrin–Fullerene Dyads Capable of Forming Charge-Separated States on a Microsecond Lifetime Scale”
Chem. Eur. J. 2014, 20, 1-15
DOI: 10.1002/chem.201404435

N.A. Danilkina, A.E. Kulyashova, A.F. Khlebnikov, S. Bräse, I.A. Balova, “Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core”
J. Org. Chem. 2014, 79(19), 9018-9045
DOI: 10.1021/jo501396s

A.F. Khlebnikov, O.A. Tomashenko, L.D. Funt, M.S. Novikov, “Simple Approach to Pyrrolylimidazole Derivatives by Azirine Ring Expansion with Imidazolium Ylides”
Org. Biomol. Chem. 2014, 12, 6598-6609
DOI: 10.1039/c4ob00865k

A.S. Konev, D.A. Lukyanov, P.S. Vlasov, O.V. Levin, A.A. Virtsev, I.M. Kislyakov, A.F. Khlebnikov, “The Implication of 1,3-Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main-Chain Porphyrin Oligomers”
Macromol. Chem. Phys. 2014, 215, 516-529
DOI: 10.1002/macp.201300679

P.V. Gushchin, M.L. Kuznetsov, M. Haukka, V.Yu. Kukushkin, “Anionic halide…alcohol clusters in the solid state”
J. Phys. Chem. A 2014, 118,, 9529-9539
DOI: 10.1021/jp506256a

A.F. Khlebnikov, M.S. Novikov, Y.G. Gorbunova, E.E. Galenko, K.I. Mikhailov, V.V. Pakalnis, M.S. Avdontceva “Isoxazolium N-ylides and 1-oxa-5-azahexa-1,3,5-trienes on the way from isoxazoles to 2H-1,3-oxazines”
Beilstein J. Org. Chem. 2014, 10, 1896-1905
DOI: 0.3762/bjoc.10.197

K.V. Zavyalov, M.S. Novikov, A.F. Khlebnikov, V.V. Pakalnis, “Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine ring expansion”
Tetrahedron 2014 2014, 70(21), 3377-3384
DOI: 10.1002/macp.201300679

A.N. Kazakova, R.O. Iakovenko, V.M. Muzalevskiy, I.A. Boyarskaya, M.S. Avdontceva, G.L. Starova, A.V. Vasilyev, V.G. Nenajdenko
“Trifluoromethylated allyl alcohols: acid-promoted reactions with arenes and unusual ‘dimerization’”

Tetrahedron Lett., 2014, 55, 6851-6855

DOI: 10.1016/j.tetlet.2014.10.083

An unusual ‘dimerization’ of CF₃-allyl alcohols [ArCH=CHCH(OH)CF₃] under the action of anhydrous FeCl₃ was found to give fluorinated indanes in 62–90% yields via the formation of intermediate allyl cations. Reactions of CF₃-allyl alcohols with arenes (Ar′H) led to CF₃-alkenes [Ar(Ar′)CHCH=CHCF₃] in 48–75% yields. The mechanisms of the transformations are discussed.

T.B. Anisimova, M. Fátima C. Guedes da Silva, V.Yu. Kukushkin, A.J. L. Pombeiro, K.V. Luzyanin

“Metal-mediated coupling of amino acid esters with isocyanides leading to new chiral acyclic aminocarbene complexes”

Dalton Trans., 2014, 43, 15861-15871

DOI: 10.1039/c4dt01917b

Metal-mediated coupling between equimolar amounts of cis-[PdCl2(CNR1)2] (1–5) and the amino acid esters L-HTyrOMe (7) or L-HProOtBu (8) proceeds at 40 °C in chloroform over ca. 6 h. The subsequent workup affords the complexes cis-[PdCl2(CNR1){C(TyrOMe)[double bond, length as m-dash]NHR1}] (R1 = Xyl 9, 2-Cl-6-Me-C6H310) or cis-[PdCl2(CNR1){C(ProOtBu)[double bond, length as m-dash]NHR1}] (R1 = Xyl 11, 2-Cl-6-Me-C6H312, Cy 13, tBu 14, 2-naphthyl 15) in good to excellent isolated yields (75–94%). The corresponding reaction between trans-[PdI2(CNR1)2] (6) and 8 brings about the formation of trans-[PdI2(CNCy){C(ProOtBu)[double bond, length as m-dash]NHCy}] (16, 76% isolated yield). The reaction of 6 with 7 proceeds non-selectively giving a broad mixture of products. Complexes 9–16 were characterized by elemental analyses (C, H, N), ESI+/−-MS, IR, 1D (1H, 13C{H}) and 2D (1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopic techniques, and by single-crystal X-ray diffraction (for 9, 11–13, and 16).

M.Ya. Demakova, K.V. Luzyanin, G.L. Starova, V.Yu. Kukushkin
“Facile alternative route to cis-[PtCl2(PTA)2] and [PtCl(PTA)3]Cl (PTA = 1,3,5-triaza-7-phosphaadamantane)”

Inorg. Chem. Commun., 2014, 50, 17-18

DOI: 10.1016/j.inoche.2014.10.002

The reaction of trans-[PtCl2(Me2SO)2] with 2 equivs of 1,3,5-triaza-7-phosphaadamantane (PTA) in MeNO₂ at RT furnished cis-[PtCl₂(PTA)₂] (1) in 87% isolated yield. Corresponding reaction of K₂[PtCl₄] with 1 equiv. of PTA in aqueous EtOH at RT led to [PtCl(PTA)₃]Cl (2) in 84% isolated yield. Complexes 1 and 2 were characterized by elemental analyses (C, H, N), HR-ESI+/−-MS, IR, ¹H and ³¹P{¹H} NMR spectroscopic techniques, and by single-crystal X-ray diffraction for 1.

D.S. Bolotin, K.I. Kulish, N.A. Bokach, G.L. Starova, V.V. Gurzhiy, V.Yu. Kukushkin

“Zinc(II)-Mediated Nitrile−Amidoxime Coupling Gives New Insights into H+‑Assisted Generation of 1,2,4-Oxadiazoles”

Inorg. Chem., 2014, 53, 10312-10324

DOI: 10.1021/ic501333s

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)). All new obtained compounds were characterized by HRESI-MS, IR, ATR-FTIR, ¹H NMR, CP-MAS TOSS ¹³C NMR, elemental analyses (C, H, N), and single crystal X-ray diffraction for seven species (3a–e, [4b](p-TolSO₃), and [4d](p-TolSO₃)). Two previously unknown heterocycles 5c and 5e were isolated and characterized by elemental analyses (C, H, N), HRESI-MS, IR, ¹H and ¹³C{¹H} NMR. The observed conversion of [4a–j](p-TolSO₃) to the 1,2,4-oxadiazoles uncovers the mechanism of the previously reported H+-assisted generation of these heterocycles (Augustine; et al. J. Org. Chem. 2009, 74, 5640).

S. Miltsov, V. Karavan, M. Goikhman, I. Podeshvo, S. Gómez-de Pedro, M. Puyol, J. Alonso-Chamarro

“Synthesis of bis-aminosubstituted indocyanine dyes for their use in polymeric compositions”

Dyes and Pigments, 2014, 109, 34-41

DOI:10.1016/j.dyepig.2014.05.002

The synthesis of a set of open-chain bis-aminosubstituted cyanine dyes as well as others with cyclic fragments in the polymethine chain is presented. These dyes are suitable for the development of polymeric compositions with variable optical characteristics as they can be covalently incorporated into the polymer.