Organolithium compounds nickel carbonyl

An acyl group can be introduced into the 4 position of an a,p-unsaturated ketone by treatment with an organolithium compound and nickel" carbonyl.546 The product is a 1,4-... 

An acyl group can be introduced into the 4 position of an a,(3-unsamrated ketone by treatment with an organolithium compound and nickel carbonyl. The product is a 1,4-diketone, 157. The R group may be aryl or primary alkyl. The reaction can also be applied to alkynes (which need not be activated), in which case 2 mol add and the product is also a 1,4-diketone (e.g., R C=CH RCOCHR CH2COR). " In a different procedure, ot,(3-unsaturated ketones and aldehydes are acylated by treatment at — 110°C with R2(CN)CuLi2 and CO. This method is successful for R = primary, secondary, and tertiary alkyl.For secondary and tertiary groups, R(CN)CuLi (which does not waste an R group) can be used instead. 

Conjugate addition of acyl groups to a,fl-unsaturated carbonyl compounds.3 Nickel carbonyl forms unstable complexes with organolithium compounds (ether,... 

Michael additions of organolithium, Grignard, and diorganozinc reagents to enones and other rt, -unsaturated carbonyl compounds are catalyzed inter alia by copper, nickel and cobalt salts. The best results are obtained with cop-per(I) catalysts, especially those in which copper is bound to a soft , readily polarizable center (sulfur or phosphorus). 

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