It's all relative: A practical and efficient PdII‐catalyzed regio‐ and chemoselective chlorination/bromination has been developed for the facile synthesis of a broad range of aromatic chlorides. The reaction demonstrates excellent reactivity, good functional‐group tolerance, and high yields. A preliminary study was conducted to evaluate relative directing‐group abilities of various functionalities.

All the hype: The title reaction has been developed for the facile synthesis of a variety of complex alkyl ethers. Cyclic hypervalent iodine (I(3+) ) reagents serve as oxidants for this unique CH alkoxylation reaction. The reaction demonstrates excellent reactivity, good functional-group tolerance, and high yields. Q=8-aminoquinoline-derived auxiliary.

A novel and efficient synthesis of 2-aminophenols, 2-aminobenzene-1,3-diols, and heterocycles through Ru-catalyzed C-H mono- and dihydroxylation of anilides has been developed with a new directing group strategy. The reaction demonstrates excellent reactivity, regioselectivity, good functional group tolerance, and high yields.

No abstract

Axially chiral 4-arylisoquinolones are endowed with pronounced bioactivity, and methods for their efficient synthesis have gained widespread attention. However, enantioselective synthesis of axially chiral 4-arylisoquinolones by means of C-H activation has not been reported to date. Described here is a rhodium (III)-catalyzed C-H bond activation and annulation for the atroposelective synthesis of axially chiral 4-arylisoquinolones. The method employs chiral cyclopentadienyl ligands embodying a piperidine ring as backbone and yields the atropisomers with good to excellent yields and enantioselectivity. Biological relevance of the 4-arylisoquinolones was demonstrated by their investigation in different cellular assays, leading to the discovery of novel non-SMO (SMO= smoothened) binding Hedgehog pathway inhibitors.

A unique Rh(II) and Ru(II) catalyzed C-H oxygenation of aryl ketones and other arenes has been developed for the facile synthesis of diverse functionalized phenols. The reaction demonstrates excellent reactivity, regio- and chemoselectivity, good functional group compatibility and high yields. The practicality of this method has been proved by gram-scale synthesis of a few different 2-acylphenols. Its utility has been well exemplified in further applications in heterocycle synthesis and direct modifications of drug Fenofibrate.

Säure bringt den Sauerstoff: Eine einfache, allgemeine Methode zur Pd‐katalysierten C‐H‐Oxygenierung liefert zahlreiche funktionalisierte Phenole ausgehend von gut zugänglichen Arylketonen, Benzoaten, Benzamiden, Acetaniliden und Sulfonamiden. Ein Lösungsmittelsystem aus Trifluoressigsäure (TFA) und TFA‐Anhydrid (TFAA) fungiert dabei als Sauerstoffquelle und ist der wesentliche Faktor für die C‐H‐Aktivierung.

A palladium(II)-catalyzed β-methylene C(sp(3))-H bond alkenylation of acyclic aliphatic amides with alkenyl halides has been developed. Both (E)-olefins and (Z)-olefins can be readily accessed using this method and a possible (Z)/(E)-olefin isomerization pathway is proposed. A solvent effect-promoted sequential C(sp(3))-H bond alkenylation and C(sp(2))-H bond alkenylation was also studied, and can provide a convenient route to novel diene compounds.