Selective oxidation reactions are challenging when carried out on an industrial scale. Many traditional methods are undesirable from an environmental or safety point of view. There is a need to develop sustainable catalytic approaches that use molecular oxygen as the terminal oxidant. This review will discuss the use of stable radicals (primarily nitroxyl radicals) in aerobic oxidation catalysis. We will discuss the important advances that have occurred in recent years, highlighting the catalytic performance, mechanistic insights and the expanding synthetic utility of these catalytic systems.

A copper(i)/ketoABNO aerobic catalyst system is highly effective for the oxidation of secondary alcohols, including unactivated aliphatic substrates. The effects of pressure and gas composition on catalyst performance are examined. The radical can be employed at low loadings and it is also amenable to immobilisation on to solid supports.

A homogeneous PdII catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2‐alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures.

The reaction of leucoquinizarin with ethylenediamine and N-al kylethylenediamines gives two series of products, 1 ,4bisa I ky I a m i n oa n t h ra q u i n o n es and 6 -a I ky lam i n o -1 ,2,3,4 -tetra h y dron a p h t h o [ 2,3f] q u i n oxa I i n e -7,12d i o n es.Higher alkylenediamines give only the 1.4-bisalkylaminoanthraquinones. Analogous reactions with 5,8-dihydrleucoquinizarin are also described. LEUCOQUINIZARIN (I) reacts with alkylamines to give characteristics in that the absorptions are shifted to 1,4-bisalkylaminoanthraquinones (11) which have shorter wavelengths, i.e., 567 and 608 mp with an inflecvisible absorption spectra in 2-methoxyethanol with tion at 530 mp and an additional peak at 435 mp (type peaks at 642 and 594 mv and an inflection at 553-556 I1 spectrum, see Figure 1 in ref. 2). In explanation rnp (type I spectrum, see Figure 1 in ref. 2). Simon re-Simon suggested that in the compounds (IIa) and (IIb) ported the preparation of two compounds of this class &signed thestructures 1,4-di-(2-aminoethylaminoanthra-F. B. Stilmar and M. A. Perkins, ' The Chemistry of Synthetic quinone (1-1~) and 1,4-di-(2-ethylaminoethylamino)-Dyes and Pigments,' ed. H.

Abstract2‐Ynamides can be synthesised through PdII catalysed oxidative carbonylation, utilising low catalyst loadings. A variety of alkynes and amines can be used to afford 2‐ynamides in high yields, whilst overcoming the drawbacks associated with previous oxidative methods, which rely on dangerous solvents and gas mixtures. The use of [NBu4]I allows the utilisation of the industrially recommended solvent ethyl acetate. O2 can be used as the terminal oxidant, and the catalyst can operate under safer conditions with low O2 concentrations.