We have described a C−H arylation/ring-transformation strategy for the synthesis of triarylpyridines, which form the core structure of thiopeptide antibiotics. This synthetic method readily gave 2,3,6-triarylpyridines in a regioselective manner by a two-phase approach: C−H arylation (a nickel-catalyzed decarbonylative Suzuki–Miyaura cross-coupling and decarbonylative C−H coupling for the synthesis of 2,4-diaryloxazoles) and ring transformation ([4+2] cycloaddition of 2,4-diaryloxazoles with (hetero)arylacrylic acids). To showcase these methods, we have accomplished the formal synthesis of thiopeptide antibiotics GE2270 s and amythiamicins.

A step-economical and stereodivergent synthesis of privileged 2-arylcyclopropylamines (ACPAs) through a C(sp³)H borylation and Suzuki–Miyaura coupling sequence has been developed. The iridium-catalyzed CH borylation of N-cyclopropylpivalamide proceeds with cis selectivity. The subsequent B-cyclopropyl Suzuki–Miyaura coupling catalyzed by [PdCl₂(dppf)]/Ag₂O proceeds with retention of configuration at the carbon center bearing the Bpin group, while epimerization at the nitrogen-bound carbon atoms of both the starting materials and products is observed under the reaction conditions. This epimerization is, however, suppressed in the presence of O₂. The present new ACPA synthesis results in not only a significant reduction in the steps required for making ACPA derivatives, but also the ability to access either isomer (cis or trans) by simply changing the atmosphere (N₂ or O₂) in the coupling stage.

A step-economical and stereodivergent synthesis of privileged 2-arylcyclopropylamines (ACPAs) through a C(sp³)H borylation and Suzuki–Miyaura coupling sequence has been developed. The iridium-catalyzed CH borylation of N-cyclopropylpivalamide proceeds with cis selectivity. The subsequent B-cyclopropyl Suzuki–Miyaura coupling catalyzed by [PdCl₂(dppf)]/Ag₂O proceeds with retention of configuration at the carbon center bearing the Bpin group, while epimerization at the nitrogen-bound carbon atoms of both the starting materials and products is observed under the reaction conditions. This epimerization is, however, suppressed in the presence of O₂. The present new ACPA synthesis results in not only a significant reduction in the steps required for making ACPA derivatives, but also the ability to access either isomer (cis or trans) by simply changing the atmosphere (N₂ or O₂) in the coupling stage.

Life-threatening infections caused by bacteria that have developed resistance to common antibiotics, such as methicillin-resistant Staphylococcus aureus (MRSA), have become a serious problem in hospitals and other areas all over the world. Thus, the development of an effective class of antibiotics against these bacteria is an urgent subject. Herein, we report a step-economical and diversity-oriented synthesis of a series of 2-arylidenehydrazinyl-4-arylthiazole and 2-arylidenehydrazinyl-5-arylthiazole analogues that utilizes C–H coupling methodologies. A library of 54 new congeners were synthesized and tested for their biological potential. Moreover, new knowledge regarding the structure–activity relationships (SARs) of these heterobiaryl compounds was collected.

The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. For this transformation, 3,4-bis(dicyclohexylphosphino)thiophene (dcypt) was identified as a new, enabling, air-stable ligand for this transformation. The intermediate of an assumed CO oxidative addition was isolated and characterized by X-ray crystal-structure analysis.

The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. For this transformation, 3,4-bis(dicyclohexylphosphino)thiophene (dcypt) was identified as a new, enabling, air-stable ligand for this transformation. The intermediate of an assumed CO oxidative addition was isolated and characterized by X-ray crystal-structure analysis.

Nickel catalysis for biaryl coupling reactions has received significant attention as a less expensive and less toxic alternative to “standard” palladium catalysis. Here we describe recent developments in nickel-catalyzed biaryl coupling methodology, along with mechanistic studies and applications. In particular we focus on nickel-catalyzed coupling reactions in which “unreactive” bonds such as C–H, C–O, and C–C bonds are converted into biaryl moieties.

The direct functionalization of CH bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon–carbon and carbon–heteroatom bonds. This Review provides an overview of CH bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

Die direkte Funktionalisierung von C-H-Bindungen in organischen Molekülen hat sich in jüngster Zeit zu einer wirksamen und idealen Methode entwickelt, mit der Kohlenstoff-Kohlenstoff- und Kohlenstoff-Heteroatom-Bindungen geknüpft werden können. Der Aufsatz gibt einen Überblick über die Strategien, die durch Funktionalisierung von C-H-Bindungen eine rasche Synthese von biologisch aktiven Verbindungen wie Naturstoffen und pharmazeutischen Zielsubstanzen ermöglichen.