Synthesis of the azocino[4,3‐b]indole core structure for the synthesis of strychnos alkaloids

The synthesis of compound 12 which has a hexahydro‐1,5‐methanoazocino[4,3‐b]indole structure for the synthesis of pentacyclic strychnos type alkaloids (tubifolin and tubifolidine) is described. Many new compounds 5–12 have also been synthesized.     

A novel synthetic approach for the synthesis of pyridocarbazole alkaloids

The synthesis of 11‐methyl‐6H‐pyrido[4,3‐b]carbazole‐1(2H)‐one (5), which can be important for the synthesis of other pyridocarbazole alkaloids and especially 1‐substituted ellipticines, is described. Construction of the tetracyclic structure was achieved by a new route and two important precursor compounds (4a and 4b) for the synthesis of pyridocarbazole alkaloids and also many new tetrahydrocar‐bazole derivatives (7, 8, 9, 10, 11, 12, 13) were synthesized.     

An entry to the azocino[4,3-b]indole framework through a dehydrogenative activation of 1,2,3,4-tetrahydrocarbazoles mediated by DDQ: formal synthesis of (±)-uleine

It is presented that hexahydro-1,5-methano[4,3-b]indoles were efficiently synthesized in high yields (up to 89% yield) through the cyclization reaction of starting tetrahydrocarbazoles bearing a monoalkylaminocarbonylmethyl moiety at the C-2 position mediated by 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). A mechanistic proposal is also given that mainly includes two cascade reactions: (i) formation of a vinylogous iminium cation via DDQ-mediated dehydrogenation of tetrahydrocarbazole functionality and (ii) intra-molecular and syn-selective addition of the amide functionality as the nucleophile to the vinylogous iminium cation. Furthermore, this cyclization reaction was successfully utilized in the formal total synthesis of (±)-uleine, an Aspidospermatan skeletal type alkaloid.     

Ion‐exchanger synthesis using reversible addition‐fragmentation chain transfer polymerization

An ion‐exchanger with polyanionic molecular brushes was synthesized by a “grafting from” route based on “surface‐controlled reversible addition‐fragmentation chain transfer polymerization” (RAFT). The RAFT agent, PhC(S)SMgBr was covalently attached to monodisperse‐porous poly(dihydroxypropyl methacrylate‐co‐ethylene dimethacrylate), poly(DHPM‐co‐EDM) particles 5.8 μm in size. The monomer, 3‐sulfopropyl methacrylate (SPM), was grafted from the surface of poly(DHPM‐co‐EDM) particles with an immobilized chain transfer agent by the proposed RAFT protocol. The degree of polymerization of SPM (i. e. the molecular length of the polyanionic ligand) on the particles was controlled by varying the molar ratio of monomer/RAFT agent. The particles carrying polyanionic molecular brushes with different lengths were tested as packing material in the separation of proteins by ion exchange chromatography. The columns packed with the particles carrying relatively longer polyanionic ligands exhibited higher separation efficiency in the separation of four proteins. Plate heights between 130–200 μm were obtained. The ion‐exchanger having poly‐(SPM) ligand with lower degree of polymerization provided better peak‐resolutions on applying a salt gradient with higher slope. The molecular length and the ion‐exchanger group content of polyionic ligand were adjusted by controlling the degree of polymerization and the grafting density, respectively. This property allowed control of the separation performance of the ion‐exchanger packing.     

Intermediates for the synthesis of indole alkaloids. Synthesis of tetrahydrocarbazole derivatives

The synthesis of new precursors 8 and 15 for the synthesis of tetracyclic indole alkaloids were described. Many new intermediates 4‐7 and 9‐14 have also been synthesized.     

Total synthesis of 5-demethylellipticine

Ethyl 1,2-dihydro-4-methylcarbazole-3-carboxylate and 11-methl-6H-pyrido[4,3-b] carbazole (5-demethylellipticine) have been synthesized by different routes.     

Highly Active Cobalt Sulfide/Carbon Nanotube Catalyst for Hydrogen Evolution at Soft Interfaces

Hydrogen evolution at polarized liquid–liquid interfaces [water/1,2‐dichloroethane (DCE)] by the electron donor decamethylferrocene (DMFc) is catalyzed efficiently by the fabricated cobalt sulfide (CoS) nanoparticles and nanocomposites of CoS nanoparticles formed on multi‐walled carbon nanotubes (CoS/CNT). The suspended CoS/CNT nanocomposite catalysts at the interface show a higher catalytic activity for the hydrogen evolution reaction (HER) than the CoS nanoparticles due to the high dispersity and conductivity of the CNT materials, which can serve as the main charge transport pathways for the injection of electrons to attain the catalytic sites of the nanoparticles. The reaction rate increased more than 1000‐fold and 300‐fold by using CoS/CNT and CoS catalysts, respectively, when compared to a non‐catalyzed reaction.     

Studies on the synthesis of the azocino[4,3‐b]indole framework and related compounds

An efficient method for the synthesis of C‐4 position alkylated azocino[4,3‐b]indole 13 and 18 is described. Reduction of compounds 5, 6, 7 and 8 yielded the corresponding alcohols. Compounds 5, 6, 7 and 8 were synthesized through several steps starting from 1 . The resulting alcohols underwent acid catalyzed ring closure to give tetracyclic azocino[4,3‐b]indole 9, 10, 11 and 12 . Finally, compounds 9 and 17 were alkylated at C‐4 position to the corresponding products 13 and 18 . The structure of the compounds 13 and 18 has been confirmed by X‐ray single crystal analysis.