Dicarbofunctionalizations of an Unactivated Alkene via Photoredox/Nickel Dual Catalysis.

1,2-Dicarbofunctionalization of unactivated olefin has been reported under photoredox/nickel dual catalysis. The mildness of the visible-light-mediated reaction allows the use of various alkyl and aryl electrophiles with several sensitive functional groups. The protocol was equally applied for late-stage diversification of drugs and biologically active molecules. Investigations elucidated the importance of photoredox/nickel dual catalysis and α-amino-radical-mediated halogen atom transfer and provided us with the nickel complexes involved in the reaction.

Photoredox/Nickel Dual Catalysis Enables the Synthesis of Alkyl Cyclopropanes via C(sp3)-C(sp3) Cross Electrophile Coupling of Unactivated Alkyl Electrophiles.

A facile synthesis of mono-, 1,1- and 1,2-disubstituted cyclopropanes via visible light-mediated photoredox/nickel dual catalysis is demonstrated. The challenging intramolecular C(sp3)-C(sp3) cross-electrophile coupling of readily available unactivated 1,3-dialkyl electrophiles was performed under mild conditions that allowed traditionally reactive functional groups to be included. Mechanistic inspection and control experiments revealed the importance of dual catalysis and that the reaction proceeds via a stepwise oxidative addition followed by an intramolecular SN2 reaction.

Recent Development of Bis-Cyclometalated Chiral-at-Iridium and Rhodium Complexes for Asymmetric Catalysis.

The field of asymmetric catalysis has been developing to access synthetically efficacious chiral molecules from the last century. Although there are many sustainable ways to produce nonracemic molecules, simplified and unique methodologies are always appreciated. In the recent developments of asymmetric catalysis, chiral-at-metal Lewis acid catalysis has been recognized as an attractive strategy. The catalysts coordinatively activate a substrate while serving the sole source of chirality by virtue of its helical environment. These configurationally stable complexes were utilized in a large number of asymmetric transformations, ranging from asymmetric Lewis acid catalysis to photoredox and electrocatalysis. Here we provide a comprehensive review of the current advancements in asymmetric catalysis utilizing iridium and rhodium-based chiral-at-metal complexes as catalysts. First, the asymmetric transformations via LUMO and HOMO activation assisted by a chiral Lewis acid catalyst are reviewed. In the second part, visible-light-induced asymmetric catalysis is summarized. The asymmetric transformation via the electricity-driven method is discussed in the final section.

Enhancing Ru(II)-Catalysis with Visible-Light-Mediated Dye-Sensitized TiO2 Photocatalysis for Oxidative C-H Olefination of Arene Carboxylic Acids at Room Temperature.

Erythrosine B sensitized TiO2 photocatalysis has been combined with Ru(II)-catalysis to accomplish an oxidative olefination/annulation of benzoic acids with activated olefins under mild conditions that tolerates useful functionalities, such as halides, free hydroxy, acetamido, etc. The morphology of the photocatalyst is unaffected during the reaction and it can be reused. Mechanistic studies favor the involvement of a photo-induced single electron transfer process.