Jian-Rong Gao

Iodine-Catalyzed 1,3-Dipolar Cycloaddition/Oxidation/Aromatization Cascade with Hydrogen Peroxide as the Terminal Oxidant: General Route to Pyrrolo[2,1-a]isoquinolines

We report a novel molecular iodine-catalyzed 1,3-dipolar cycloaddition/oxidation/aromatization cascade process with hydrogen peroxide as the terminal oxidant for the construction of pyrrolo[2,1-a]isoquinolines. The product pyrrolo[2,1-a]isoquinolines were obtained from reactions between simple, readily available dipolarophiles and tetrahydroisoquinolines in moderate to excellent yields without the need for a metal catalyst.

Indolizine Synthesis via Oxidative Cross-Coupling/Cyclization of Alkenes and 2-(Pyridin-2-yl)acetate Derivatives.

A novel copper/I2-mediated oxidative cross-coupling/cyclization of 2-(pyridin-2-yl)acetate derivatives and simple olefins is developed, which provides a straightforward and efficient access to structural diversely indolizines. A series of 1,3-di- and 1,2,3-trisubstituted indolizines are easily synthesized in modest to excellent yields.

Iodine-Promoted Construction of Polysubstituted 2,3-Dihydropyrroles from Chalcones and β-Enamine Ketones (Esters)

A novel approach for the synthesis of a variety of polysubstituted trans-2,3-dihydropyrroles from a wide range of chalcones and β-enamine ketones (esters) via iodine-promoted tandem Michael/cyclization sequence has been developed, affording the desired products in moderate to excellent yields. This methodology is a highly efficient, convenient way to access functionalized 2,3-dihydropyrroles from readily accessible substrates under mild reaction conditions.

Palladium/l-Proline-Catalyzed Enantioselective α-Arylative Desymmetrization of Cyclohexanones

A highly enantioselective palladium/l-proline-catalyzed α-arylative desymmetrization of cyclohexanones was developed. The new strategy for α-arylation reaction led to a series of optically active morphan derivatives bearing α-carbonyl tertiary stereocenters in good yields with excellent enantioselectivities (up to 99% ee).

The synthesis of benzo[f]isoindole-1,3-dicarboxylates via an i2-induced 1,3-dipolar cycloaddition reaction.

An I2-induced 1,3-dipolar cycloaddition reaction has been developed for the synthesis of benzo[f]isoindole-1,3-dicarboxylates from quinones and N-substituted amino esters. The reaction proceeds in good to excellent yields in one step from 3 equiv of amino ester to react with the quinone structure. The utility of this transformation has been highlighted by its use for the construction of benzo[f]isoindole-1,3-dicarboxylates, which have been identified in natural products exhibiting important biological activities.

Cu(I)-Catalyzed Enantioselective Friedel–Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents

A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

Enantioselective Friedel–Crafts Alkylation Reactions of 3-Substituted Indoles with Electron-Deficient Alkenes

Highly enantioselective Friedel-Crafts C2-alkylation reactions of 3-substituted indoles with α,β-unsaturated esters and nitroalkenes were developed using chiral Lewis acids as catalysts, which afforded chiral indole derivatives bearing C2-benzylic stereogenic centers in good to excellent yields (up to 99%) and enantioselectivities (up to 96% ee).

Bifunctionalisation of 1,4-naphthoquinone by the oxidative addition of an alkylamine and iodine

Novel 2-iodo-3-(alkylamino) naphthalene-1,4-diones are formed in 33–70% yield by the reaction of alkylamine and 1, 4-naphthoquinone in the presence of iodine.

Lewis Acid Catalyzed Friedel–Crafts Alkylation of Alkenes with Trifluoropyruvates

A Friedel-Crafts alkylation reaction of styrenes with trifluoropyruvates has been developed, which delivered allylic alcohols in excellent yields (up to 98%) using the Ni(ClO4)2·6H2O/bipyridine complex as a catalyst. The asymmetric reaction was catalyzed by the chiral Cu(OTf)2/bisoxazoline complex to afford the corresponding chiral allylic alcohols bearing trifluoromethylated quaternary stereogenic centers in moderate enantioselectivities (up to 75% ee).

Solvent-free synthesis of 2-aminothiophene-3-carbonitrile derivatives using high-speed vibration milling

The solvent-free synthesis of 2-aminothiophene-3-carbonitrile derivatives by high-speed vibration milling using the inexpensive and environmentally friendly Et2NH as a catalyst was studied. The reaction conditions were optimised and the derivatives were obtained in good yield. This method has advantages in terms of short reaction time and facile conditions.