The decarboxylative Blaise reaction.

Reaction of aryl nitriles with potassium ethyl malonate in the presence of zinc chloride and a catalytic amount of Hünig's base provided beta-amino acrylates in moderate to good yield. Compared to the classical Blaise reaction, this reaction is safer (endothermic), devoid of lacrimatory reagent, and is possible with 0.5-1.

Asymmetric catalysis of the [5 + 2] cycloaddition reaction of vinylcyclopropanes and pi-systems.

As part of our studies of metal-catalyzed [m + n (+...

Tin-Free Radical Acylation Reactions with Methanesulfonyl Oxime Ether.

A simple strategy involving thermal decomposition of the methanesulfonyl radical into the methyl radical and the subsequent transfer of an iodine atom or phenyl telluride group was used to develop a tin-free radical acylation reaction (see scheme; V-40=1,1'-azobis(cyclohexane-1-carbonitrile). The key was finding reaction conditions under which the I or PhTe transfer is faster than the direct addition of the alkyl radical to the methanesulfonyl oxime ether.