Ru(OH) x /Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensur...

A method for synthesis without protecting groups of bis(indolyl)methanes by the (η-benzyl)palladium system generated from a palladium catalyst and benzyl alcohol in water is developed. This domino protocol involves C3–H bond activation/benzylation of indole–carboxylic acids and benzylic C–H functionalization. Mechanistic studies indicate that the (η-benzyl)palladium(II) complex, which is formed...

With the increasing concern for sustainability, the use of environmentally friendly media to perform chemical processes has attracted the attention of many research groups. Among them, the use of water, as the unique solvent for reactions, is currently an active area of research. One process of particular interest is the direct nucleophilic substitution of an alcohol avoiding its preliminary tr...

Pd(OAc)(2) in DMSO is an effective catalyst for the aerobic oxidation of alcohols and numerous other organic substrates. Kinetic studies of the catalytic oxidation of primary and secondary benzylic alcohol substrates provide fundamental insights into the catalytic mechanism. In contrast to the conclusion reached in our earlier study (J. Am. Chem. Soc. 2002, 124, 766-767), we find that Pd(II)-me...

We report here a base free copper(I) catalyst for the selective aerobic oxidation of primary alcohols to their corresponding aldehydes and various diols lactones or lactols. In presence in situ generated Cu(I)-catalyst with 2,2′-dipyridylamine (dpa) as ligand 2,2,6,6-tetramethylpiperdine-N-oxyl (TEMPO) persistent radical, reaction proceeds under true conditions, at ambient temperature, utilizin...

Cu/nitroxyl catalysts have been identified that promote highly efficient and selective aerobic oxidative lactonization of diols under mild reaction conditions using ambient air as the oxidant. The chemo- and regioselectivity of the reaction may be tuned by changing the identity of the nitroxyl cocatalyst. A Cu/ABNO catalyst system (ABNO = 9-azabicyclo[3.3.1]nonan-N-oxyl) shows excellent reactiv...

To expand upon the recent pioneering reports of catalyzed sp(3) C-H fluorination methods, the next rational step is to focus on directing "radical-based fluorination" more effectively. One potential solution entails selective C-C bond activation as a prelude to selective fluorination. Herein, we report the tandem photocatalyzed ring-opening/fluorination reactions of cyclopropanols by 1,2,4,5-te...

A series of 4-pyrrolidinopyridine (4-PPY) C-3 carboxamides containing peptide-based side chains have been synthesised and evaluated in the kinetic resolution of a small library of chiral benzylic secondary alcohols. A key design element was the incorporation of a tryptophan residue in the peptide side chain for promoting π-stacking between peptide side chain and the pyridinium ring of the N-acy...

A series of aromatic hydrocarbons were investigated so as to compare the reactivity of corannulene with planar aromatic hydrocarbons. Corannulene was found to be more reactive than benzene, naphthalene and triphenylene to Friedel-Crafts acylation whilst electrophilic aromatic bromination was also used to confirm that triphenylene was less reactive than corannulene and that pyrene, perylene and ...

We report the structural and functional features of two new catalysts: a mononuclear [Fe(N5mpy)(CH3CN)] (BF4)2 (N5mpy = (N,N 0E,N,N0E)-N,N0-(pyridine-2,6-diylbis (ethan-1-yl-1-ylidene))bis(1-(pyridin-2-yl)methanamine)) complex and a binuclear {[Fe(N5mpy)]2O}(BF4)4 complex. Both compounds catalyze the oxidation of alkanes by H2O2, in MeCN or acetone to yield alcohols and ketones. Moderate to goo...