A three-component iodine-catalyzed oxidative coupling reaction: a heterodifunctionalization of 3-methylindoles.

A metal-free method for the synthesis of heterodifunctional indole derivatives is developed through TBHP/KI-mediated oxidative coupling. The reaction constructs C-O and C-C bonds in succession with the help of tert-butyl peroxy radicals generated by the TBHP/KI catalytic system, enabling the direct realization of the heterodifunctionalization of indole in one pot. The product of this reaction is a novel heterodifunctional compound. This work might provide a new effective method for the synthesis of polycyclic indole compounds.

Selectfluor facilitated bridging of indoles to bis(indolyl)methanes using methyl tert-butyl ether as a new methylene precursor.

A novel, green and efficient method is developed for the synthesis of methylene bridged bis(indolyl)methanes in good to excellent yields. The reaction employs methyl tert-butyl ether (MTBE) as the methylene source and selectfluor as an oxidizing agent. The scope and versatility of the methods have been successfully demonstrated with 48 examples. The metal-free transformation process is suitable for scale-up production. A selectfluor-promoted oxidative reaction mechanism is proposed based on the results of the experimental studies.

Condensation of acrylonitrile and aryl acetonitrile: construction of α-amino-ß-cyano cyclohexene skeletons.

A representative condensation of acrylonitrile and aryl acetonitrile has been reported for the synthesis of α-amino-ß-cyano cyclohexene. The reaction was carried out mildly in an open environment at room temperature. The scope and versatility of the method have been demonstrated with 20 examples, containing highly active ethynyl groups. Further applications for 4-aminopyrimidine compounds were performed. A mechanism was proposed, involving Michael additions between acrylonitrile and aryl acetonitriles as well as intramolecular condensation.

Iodine-Mediated Pyridine Ring Expansion for the Construction of Azepines.

A synthesis of azepines by the expansion of pyridine rings promoted by iodine in air is reported. The scope of the method is demonstrated with 27 examples. Two iodinations are involved in the reaction, in which the second iodination leads to the opening of the six-membered ring.

Copper(II)-hydroxide facilitated C-C bond formation: the carboxamido pyridine system versus the methylimino pyridine system.

A copper(ii)-hydroxide-induced carbon-carbon bond formation reaction is explored with the synthesis of an asymmetric carboxamido-methylimino pyridine Cu(i) complex of [CuI(py(N-C[double bond, length as m-dash]O)(N[double bond, length as m-dash]C-C)ph2Me2)2]- (12). Two imine-methyl groups are coupled to form a bridged C-C bond (N[double bond, length as m-dash]C-C-C-C[double bond, length as m-dash]N) at the methyl positions with the reduction of two Cu2+ center ions to Cu+. The reaction is checked with three dicarboxamido pyridine [CuII-OH] complexes, with which dinuclear Cu(i) complexes of [Cu2(py(N-C[double bond, length as m-dash]O)2ph2R2)2]2- (R = methyl (3), methyl and allyl (6)) and trinuclear [CuII-CuI-CuII] complex of [Cu3(⊂20-py(N-C[double bond, length as m-dash]O)2ph2dienMe3)2]+ (9) are obtained. The reactivities of the [CuII-L] (L = DMF, OH-) complexes in dicarboxamido pyridine, carboxamido-methylimino pyridine and dimethylimino pyridine systems are discussed in terms of the electron delocalization properties of ligands. A cooperative metal-ligand (Cu2+ and enamide ligand) interaction is proposed based on the characterization of ligated Cu(ii) intermediates with the techniques of X-ray crystallography, UV-vis spectroscopy, cyclic voltammogram, EPR spectroscopy, and DFT calculations.

Temperature controlled condensation of nitriles: efficient and convenient synthesis of ß-enaminonitriles, 4-aminopyrimidines and 4-amidinopyrimidines in one system.

A series of ß-enaminonitriles, 4-aminopyrimidines and 4-amidinopyrimidines were synthesized by condensation of organonitriles in one system. A wide variety of compounds were obtained in good to excellent yields by simply controlling the reaction temperature. The base-induced transformation process is easy for production. The scope and versatility of the method have been successfully demonstrated with 72 examples. The flexible and diversified characteristics of nitriles were introduced based on electronic effect, steric effect, position of substituted groups and intermolecular hydrogen bonding. An updated reaction mechanism is proposed based on the study of the stoichiometric reaction conditions at variable temperature, and on the investigation of products with cis-trans configuration transformation.

Copper(II)-Dioxygen Facilitated Activation of Nitromethane: Nitrogen Donors for the Synthesis of Substituted 2-Hydroxyimino-2-phenylacetonitriles and Phthalimides.

A simple and efficient method is explored for the synthesis of 2-hydroxyimino-2-phenylacetonitriles (2) and phthalimides (4), by using nitromethane as nitrogen donors. Both reactions are promoted by Cu(II) system with the participation of dioxygen as an oxidant. The scope of the method has been successfully demonstrated with a total of 51 examples. The flexible and diversified characteristics of reactions are introduced in terms of electronic effect, steric effect, position of substituted groups, and intramolecular charge transfer. Experimental studies suggest that the methyl nitrite could be a precursor in the path to the final products. A possible reaction mechanism is proposed, including the Cu(II)/O2-facilitated transformation of nitromethane to methyl nitrite, the base-induced formation of 2-hydroxyimino-2-phenylacetonitriles, and the base-dioxygen-promoted formation of phthalimides.