Studies on Nitro Carboxylic Acids. II. Synthesis of α,β-Unsaturated β-Nitro Carboxylic Esters

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(...

Oxidative cleavage of unsaturated carboxylic acids (US)

Iron-catalysed green synthesis of carboxylic esters by the intermolecular addition of carboxylic acids to alkenes.

Iron triflate, in situ-formed from FeCl3 and triflic acid, or FeCl3 and silver triflate efficiently catalyse the intermolecular addition of carboxylic acids to various alkenes to yield carboxylic esters; the reaction is applicable to the synthesis of unstable esters, such as acrylates.

PhI(OAc)2 mediated decarboxylative sulfonylation of β-aryl-α,β-unsaturated carboxylic acids: a synthesis of (E)-vinyl sulfones.

A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl sulfones from of β-aryl-α,β-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)benzene (PhI(OAc)2) was developed. This strategy offers a simple and expedient synthesis of (E)-vinyl sulfones bearing a wide variety of functional groups. A radical-based pathway has been propos...

Oxidative cleavage of unsaturated carboxylic acids (US CON)