Nickel acetylacetonate catalysis

Lithium477 and potassium478 enolates of P-dicarbonyl compounds are aminated by azodicarboxylic esters in good to excellent yields. Diethyl malonate, ethyl acetoacetate, /V,/V-diethyI acetoacetamide, and acetylacetone have also been aminated with diethyl azodicarboxylate under nickel acetylacetonate catalysis,479 and nickel salicylideneimine complexes catalyze the analogous amination of acetylacetone and its 2-methyl derivative.480... 

Metal catalysed cyclopropanation using other types of intermediate is also possible. Lithiated tert-butyl alkyl sulphones bring about the cyclopropanation of various nonactivated alkenes under nickel(II) acetylacetonate catalysis (equation 88)131,132. Sulphonium ylides of type 90 react with simple alkenes under copper catalysis to give the corresponding cyclopropane adduct (equation 89)113,134. In this example the ylide (90) is the sulphonium equivalent of ethyl diazoacetate134. 

The second chapter of the book covered the advances in enantioselective nickel(ii)-catalysed conjugate additions. An important breakthrough in the history of the Michael reaction was the achievement of the Michael addition of p-dicarbonyl compounds to a broad variety of electrophiles catalysed by nickel acetylacetonate, described by Nelson in 1979-1980. Since this pioneering contribution, nickel has become one of the preferred metals in catalytic Michael reactions. Later, in 1988, Soai developed the first asymmetric conjugate additions performed under chiral nickel(ii) catalysis. Ever since. 

The extraordinary behavior of cobalt in coordinate catalysis is also evident from Figure 1. Nickel and cobalt acetylacetonate in the presence... 

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