The regioselective mercuration of tetraalkylated calix[4]arenes with Hg(OCOCF3)2 leads to the formation of meta-substituted products which enabled Pd-catalysed intramolecular bridging within the calixarene skeleton. Bridged derivatives represent a completely novel substitution pattern in calixarene chemistry with extremely distorted cavities and possible applications in supramolecular chemistry.

A neutral metallo-cavitand based on cis bis-perhaloaryl Pd(II) bridges co-ordinated at the corners of a deep calix[4]arene. Both the metallo-cavitand and its inclusion complexes with other calix[4]arenes were investigated by means of (1)H and (19)F NMR experiments.

The first palladium-catalyzed direct monofluoromethylation of arylboronic esters to produce monofluoromethyl arenes is reported. The reaction is typically carried out at room temperature within 4 h and has a good functional group tolerance. The monofluoromethylating agent, CH2FI, was readily prepared via a halogen-exchange process.

Addition of functionalized aryl, heteroaryl or adamantyl zinc reagents to various nitroso-arenes in the presence of magnesium salts and LiCl in THF produces after a reductive work-up with FeCl2 and NaBH4 in ethanol the corresponding polyfunctional secondary amines in high yields.

A novel visible light mediated radical cyclization of enol lactones with difluoroacyl arenes is presented. The reaction experienced a tandem radical cyclization and tolerated a wide range of substrates, resulting in fluorinated γ-butyrolactones in good chemical yield and with excellent diastereoselectivity.

The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc)2/molybdovanadophosphoric acid (HPMoV) as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

n-Butyllithium/N,N,N',N'-tetramethylethylenediamine-mediated ortholithiations of aryloxazolines are described. Methyl substituents on the aryloxazoline and substituents at the meta position of the arenes (methoxy, oxazolinyl, and fluoro) influence the rates and the mechanisms. Monomer- and dimer-based reactions are implicated. Density functional calculations probe details of the mechanism and s...

Pd(II)-catalyzed intramolecular amination of arenes is developed using either a one- or two-electron oxidant. The reaction protocol tolerates a wide range of deactivating groups including acetyl, cyano, and nitro groups. This catalytic reaction allows expedient syntheses of broadly useful substituted indolines or indoles.

The rhodium(III)-catalyzed hydroarylation of internal alkynes is described. Good yields are obtained for a variety of alkynes, and excellent regioselectivity is observed for unsymmetrically substituted alkynes. The reaction also gives good yields for a range of arenes. Preliminary mechanistic investigations suggest that this reaction proceeds through arene metalation with the cationic rhodium c...

Iodoarylation of arylacetylenes was performed using a simple reagent system composed of molecular iodine and [bis(benzoyloxy)iodo]benzene. Most arylacetylenes efficiently underwent the iodoarylation reaction with electron-rich arenes to give trans 1,1-diaryl-2-iodoethene adducts regio- and stereoselectively. As an exception, the iodoarylation of p-methoxyphenylacetylene resulted in a mixture of...