A cationic cobalt(III)-catalyzed direct CH amidation of unactivated (hetero)arenes and alkenes by using 1,4,2-dioxazol-5-ones as the amidating reagent has been developed. This transformation proceeds efficiently under external oxidant-free conditions with a broad substrate scope. Moreover, 6-arylpurine compounds, which often exhibit high potency in antimycobacterial, cytostatic, and anti-HCV activities, can be smoothly amidated, thus offering a mild protocol for their late stage functionalization.

A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O₂, which makes this method practical for further applications.

An efficient method for the synthesis of quinoxaline N-oxides proceeds by the dehydrogenative N-incorporation of simple imines by C(sp²)H and C(sp³)H bond functionalization. The overall transformation involves the cleavage of three CH bonds. The reaction is easily handled and proceeds under mild conditions. Simple and readily available tert-butyl nitrite (TBN) was employed as the NO source.

An efficient method for the synthesis of quinoxaline N-oxides proceeds by the dehydrogenative N-incorporation of simple imines by C(sp²)H and C(sp³)H bond functionalization. The overall transformation involves the cleavage of three CH bonds. The reaction is easily handled and proceeds under mild conditions. Simple and readily available tert-butyl nitrite (TBN) was employed as the NO source.

A novel copper-catalyzed aerobic oxidative C(CO)C(alkyl) bond cleavage reaction of aryl alkyl ketones for CN bond formation is described. A series of acetophenone derivatives as well as more challenging aryl ketones with long-chain alkyl substituents could be selectively cleaved and converted into the corresponding amides, which are frequently found in biologically active compounds and pharmaceuticals.

A transition-metal-free Cs₂CO₃-catalyzed α-hydroxylation of carbonyl compounds with O₂ as the oxygen source is described. This reaction provides an efficient approach to tertiary α-hydroxycarbonyl compounds, which are highly valued chemicals and widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very environmentally friendly and practical. This transformation is highly efficient and highly selective for tertiary C(sp³)H bond cleavage.

A novel copper-catalyzed aerobic oxidative C(CO)C(alkyl) bond cleavage reaction of aryl alkyl ketones for CN bond formation is described. A series of acetophenone derivatives as well as more challenging aryl ketones with long-chain alkyl substituents could be selectively cleaved and converted into the corresponding amides, which are frequently found in biologically active compounds and pharmaceuticals.

A transition-metal-free Cs₂CO₃-catalyzed α-hydroxylation of carbonyl compounds with O₂ as the oxygen source is described. This reaction provides an efficient approach to tertiary α-hydroxycarbonyl compounds, which are highly valued chemicals and widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very environmentally friendly and practical. This transformation is highly efficient and highly selective for tertiary C(sp³)H bond cleavage.

A concise copper(I)-catalyzed oxidative transformation of aryl propargyl azides to aryl propiolonitriles has been developed. Aryl propiolonitrile derivatives can be obtained in moderate to good yields by this strategy. An oxidative Schmidt rearrangement is involved in this transformation.

A novel copper-catalyzed, multiple oxidative dehydrogenative functionalization of arylacetaldehydes leading to 2-oxo-acetamidine compounds has been developed. This transformation is highly efficient with dissociation of six hydrogens including two sp³ CH and one sp² CH bond activations. This method not only provides an efficient approach to 2-oxo-acetamidine compounds, but also offers a valuable mechanistic insight into this novel copper catalysis.

A rhodium(III)-catalyzed direct dehydrogenative annulation of benzamides with alkynes through chelating-assisted CH activation has been developed. Naphthylamide and isoquinolinone derivatives can be chemoselectively obtained by this protocol.

Often used as a common solvent for chemical reations and utilized widely in industry as a reagent, N,N-dimethylformamide (DMF) has played an important role in organic synthesis for a long time. Numerous highly useful articles and reviews discussing its utilizations have been published. With a focus on the performance of DMF as a multipurpose precursor for various units in numerous reactions, this Minireview summarizes recent developments in the employment of DMF in the fields of formylation, aminocarbonylation, amination, amidation, and cyanation, as well as its reaction with arynes.

Die organische Synthese profitiert seit langem von N,N-Dimethylformamid (DMF), das als Lösungsmittel für chemische Reaktionen und industriell auch als Reagens breit eingesetzt wird. Zu diesen Anwendungen sind bereits zahlreiche hilfreiche Artikel und Übersichten erschienen. Dieser Kurzaufsatz fasst die Verwendung von DMF als Allzweckvorstufe zusammen und stellt die neuen Entwicklungen bei Formylierungen, Aminocarbonylierungen, Aminierungen, Amidierungen, Cyanierungen und in der Reaktion mit Arinen vor.