Xiao-Ye Yu

Visible‐Light‐Driven Aza‐ortho‐quinone Methide Generation for the Synthesis of Indoles in a Multicomponent Reaction

A visible-light-driven radical-mediated strategy for the in situ generation of aza-ortho-quinone methides from 2-vinyl-substituted anilines and alkyl radical precursors is described. This process enables an efficient multicomponent reaction of 2-vinylanilines, halides, and sulfur ylides, and has a wide substrate scope and good functional group tolerance. Treatment of the cycloaddition products with a base leads to densely functionalized indoles in a single-flask operation.

A Visible‐Light‐Driven Iminyl Radical‐Mediated C−C Single Bond Cleavage/Radical Addition Cascade of Oxime Esters

A room-temperature, visible-light-driven N-centered iminyl radical-mediated and redox-neutral C-C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has been accomplished. The strategy tolerates a wide range of O-acyl oximes and unsaturated systems, such as alkenes, silyl enol ethers, alkynes, and isonitrile, enabling highly selective formation of various chemical bonds. This method thus provides an efficient approach to various diversely substituted cyano-containing alkenes, ketones, carbocycles, and heterocycles.

Catalytic Asymmetric Cycloaddition of In Situ-Generated ortho-Quinone Methides and Azlactones by a Triple Brønsted Acid Activation Strategy.

A convergent and highly stereoselective [4+2] cycloaddition of in situ-generated ortho-Quinone methides (o-QMs) and azlactone enols has been successfully developed through a triple Brønsted acid catalysis strategy. This protocol provides an efficient and mild access to various densely functionalized dihydrocoumarins bearing adjacent quaternary and tertiary stereogenic centers in high yields with excellent diastereo- and enantioselectivity.

Enantioselective direct functionalization of indoles by Pd/sulfoxide-phosphine-catalyzed N-allylic alkylation.

A general and efficient Pd/sulfoxide-phosphine complex-catalyzed direct asymmetric N-allylic alkylation of indoles has been developed to allow for the preparation of various N-allylated indoles in generally good yields with excellent enantioselectivities. This catalytic system could also be extended to other N-containing heterocycles with good results.

Dual Photoredox/Nickel-Catalyzed Regioselective Cross-Coupling of 2-Arylaziridines and Potassium Benzyltrifluoroborates: Synthesis of β-Substitued Amines

A dual visible light photoredox and nickel-catalyzed cross-coupling reaction of 2-arylaziridines and potassium benzyltrifluoroborates is described for the first time. This strategy features high functional group tolerance, exclusive regioselectivity for reaction at the more hindered C-N bond, easily accessible substrates, and mild redox-neutral reaction conditions. A variety of diversely substituted β-substituted amines are obtained in generally good yields.

Copper-Catalyzed Radical Cross-Coupling of Redox-Active Oxime Esters, Styrenes, and Boronic Acids

A visible-light-driven, copper-catalyzed three-component radical cross-coupling of oxime esters, styrenes, and boronic acids has been developed. Key steps of this protocol involve catalytic generation of an iminyl radical from a redox-active oxime ester and subsequent C-C bond cleavage to generate a cyanoalkyl radical. Upon its addition to styrene, the newly formed benzylic radical undergoes coupling with a boronic-acid-derived ArCuII complex to achieve 1,1-diarylmethane-containing alkylnitriles.