Nickel-catalyzed arylcyanation of alkenes via cyano group translocation:access to 1,n-dinitriles or 4-amino nitriles

Herein,a nickel-catalyzed arylcyanation of unactivated alkenes via cyano group translocation with aryl boronic acids has been developed.These transformations provided a robust approach to constructing structurally diverse 1,n-dinitriles or 4-amino nitriles from easily prepared and commercially available starting materials.The cyano group translocation was achieved,involving the addition into the intramolecular C–N triple bond followed by the retro-Thorpe reaction.Mechanistic studies revealed that high temperature and CsHCO_(3) as the base were crucial for the cyano group translocation.

Palladium-catalyzed vinylation of indoles with vinyl ethers via deoxygenative coupling

Indole is a promising heteroarene in many natural products and pharmaceuticals;therefore, various synthetic methods for indole functionalizations have arisen in recent years. Herein, we report a Pd-catalyzed deoxygenative coupling for the N-vinylation of indoles by employing vinyl ethers. The vinylated indoles could be readily prepared in good to excellent yields with N1-regioselectivity regardless of the electronic characteristics and substitution patterns of indole substrates. Some indole-based pharmaceutical molecules, such as gramine, evodiamine, rutaecarpine, and melatonine, are also successfully vinylated. Moreover, carbazoles and indazoles are shown to participate. Additionally, vinylated indole can readily transform into structurally interesting indole derivatives.

Controlled Synthesis of Proton-Conductive Porous Organic Polymer Gels via Electrostatically Stabilized Colloidal Formation

Porous organic polymers(POPs)have attracted extensive interest due to their structural diversity and predesigned functionality.However,the majority of POPs are synthesized as insoluble and unprocessable powders,which greatly impede their advanced applications because of limited mass transport and inadaptation for device integration.Herein,we report a controlled synthetic strategy of macroscopic POP gels by a cation-stabilized colloidal formation mechanism,which is widely adaptable to a large variety of tetra-/tri-amino build blocks for the synthesis of Tröger’s base-linked POP gels,aerogels,and ionic gels.The POP gels combined the integrated advantages of hierarchically porous structures and tailorable mechanical stiffness,whereas they could load substantial amounts of phosphoric acids and construct unimpeded transport pathways for proton conduction,exhibiting unprecedented proton conductivity at subzero temperatures.Our strategy offers a new solution to the intractable processing issues of POPs toward device applications with cutting-edge performances.

Redox-neutral ipso/ortho alkenylcyanation of(hetero)arylboronic acid enabled by 1,4-rhodium migration and fragmentation

A mild,chemoselective,redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported.A variety of 2-vinyl arylnitriles are obtained in good yields(51examples,ava.69%yields)through this strategy,which is characterized by its broad substrate scope,great functional group tolerance,and mild conditions.Mechanism studies indicate that the fragmentation is temperature dependent.The primary asymmetric exploration for the non-fragmentation product already shows promising results.The separation of the two cyano groups of homopropargylic malononitriles results in the formation of aromatic nitrile and aliphatic nitrile in one molecule,which enables the further transformations of the products.