Local reactivity descriptors to decipher the electrochemical hydrogenation of unsaturated carboxylic acids

Neutral iridium catalysts with chiral phosphine-carboxy ligands for asymmetric hydrogenation of unsaturated carboxylic acids.

We developed neutral iridium catalysts with chiral spiro phosphine-carboxy ligands (SpiroCAP) for asymmetric hydrogenation of unsaturated carboxylic acids. Different from the cationic Crabtree-type catalysts, the iridium catalysts with chiral spiro phosphine-carboxy ligands are neutral and do not require the use of a tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF-) counterion, which is ne...

Oxidative cleavage of unsaturated carboxylic acids (US)

Separability of local reactivity descriptors

The size-dependence of different local reactivity descriptors of dimer A2 and AB type of systems is discussed. We derive analytic results of these descriptors calculated using finite difference approximation. In particular, we studied Fukui functions, relative electrophilicity and relative nucleophilicity, local softness and local philicity. The results are explained using the example of the di...

Oxidative cleavage of unsaturated carboxylic acids (US CON)

A nitro-hunsdiecker reaction: from unsaturated carboxylic acids to nitrostyrenes and nitroarenes.

[reaction: see text] The nitrodecarboxylation of aromatic alpha,beta-unsaturated carboxylic acids and ring-activated benzoic acids can be achieved using nitric acid (3 equiv) and catalytic AIBN (2 mol %) in MeCN. From the effect of various additives, the nitrodecarboxylation is postulated to involve the generation of an acyloxy radical RCO(2)(*) by a NO(3)(*) radical followed by attack of a NO(...