Synthesis of 2,2′-bipyrrole-5-carboxaldehydes and their application in the synthesis of B-ring functionalized prodiginines and tambjamines

Facile, versatile, and cost-effective synthetic routes for the preparation of a range of new 3-alkyl-, 4-alkyl-, 3,4-dialkyl-, and 3-halo-4-alkyl-2,2′-bipyrrole-5-carboxaldehydes have been developed. These 2,2′-bipyrrole-5-carboxaldehydes offer interesting potential as building blocks for making bioactive natural and unnatural products, as demonstrated by the synthesis of B-ring functionalized prodiginines (PGs) and tambjamines.     

Platanus acerifolia’s buds: additional non-polar metabolites and structure revision of two previous dihydrochalcone-like metabolites

In addition to the methylated and prenylated flavonoids previously reported from Platanus acerifolia, the multistep chromatographic processing of the n-hexane extract of the fresh unripe buds resulted in the isolation of 11 metabolites. Besides six common wax constituents, the n-hexane portion led to the isolation of four gem-dimethylpyrano flavanones. They corresponded to two pairs of angular and linear isomers derived only from pinocembrin (5,7-dihydroxyflavanone). Additionally, a novel β-decadione was split into the major keto-enol tautomer as shown by the detailed NMR and EIMS analyses. Moreover, the structures of grenoblone and 4-hydroxygrenoblone, two previously reported dihydrochalcone-like metabolites, were revised according to the EIMS spectra.     

Molecular structure of potassium [N,N′-bis(salicylideneamino)nitroguanidonate-N,N′,-O,O′]nickel(ii), the product of condensation of (salicylideneamino)nitroguanidine with salicylaldehyde on a Ni2+ ion template

The crystal structure of the product of the condensation of (salicylideneamino)nitroguanidine with salicylaldehyde on a Ni²⁺ ion template, K[Ni(C₁₅H₁₀N₅O₄)] · DMF, has been studied. It was established that a planar Ni complex, consisting of isolated [NiL]^– anions and solvated [K⁺ · DMF] cations, is formed. The negative charge of the anion is localized mainly on the O atoms of the nitro group. The nitroguanidine fragment of the ligand occurs in the tautomeric form, which was not reported previously.Deceased in 1995Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2273–2277, September, 1996.     

Macrocycle opening in crown ethers

Macrocycle opening in derivatives of benzocrown ethers under the action of amines is affected by the nature of the heteroatoms in the macrocycle, the nature of the functional group in the benzene ring of the crown ether, and the length, branching, and number of hydrocarbon radicals at the amine nitrogen atom. A distinguishing feature of this reaction is the template effect of MeNH₃ ⁺, Me₂NH₂ ⁺, Na⁺, and K⁺ ions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 687–692, March, 1996.For Part I see Ref. 1.     

Synthesis and crystal structure of a pyrazole derivative of artemisia ketone

The oxime of artemisia ketone is smoothly converted to the pyrazole derivative by sodium nitrite and acetic acid in CHCl₃. The structure of the pyrazole was found by x-ray structural analysis. The PMR and¹³C NMR spectra were interpreted using two-dimensional¹H–¹³C NMR (COSY, COLOC).Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 121–123, March–April, 2000.     

Novel type of heterogenized CuCl2 catalytic systems for oxidative carbonylation of methanol

A novel type of heterogenized CuCl₂ catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl^– while keeping the catalytic activity of the homogeneous CuCl₂ catalyst, we adopted, as supports (or ligands) of CuCl₂, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl₂ and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl₂ and Ppy-CuCl₂ catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl₂ catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl₂ catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl₂ leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system.     

A new method for the synthesis of the marine alkaloid fascaplysin

A new method for the synthesis of the marine alkaloid fascaplysin has been developed via a simple and practical approach to pyrido[1,2-a:3,4-b′]diindole ring system formation. Conversion of the marine alkaloid homofascaplysin C into fascaplysin is also described.     

Animal bone meal as an efficient catalyst for crossed-aldol condensation

α,α′-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in water by using animal bone meal (ABM) or ABM modified as a catalyst. It is shown that ABM modified can be quantitatively recovered and be reused effectively for many times. A comparison of catalytic activity of these catalysts is discussed.