Oxygen carbon bond activation reactions

Carbon-carbon bond formation reactions are of critical importance to the Fischer Tropsch synthesis of linear hydrocarbons over transition metals such as Co, Fe or Ru. Fischer-Tropsch synthesis involves the activation of CO and H2 over the metal to form adsorbed carbon, oxygen and hydrogen. The carbon atoms that form hydrogenate to form... 

Reaction of 6 with tertiary and also certain secondary enamines leads to the formation of 3-amino-benzo[fc]furan derivatives 174. This is formed not by Michael addition, but via geminate radical ion pair formation with subsequent generation of an oxygen-carbon bond to yield benzofurans. The products were investigated with regard to inhibition of purified human protein kinase CK2 and their general cytostatic activity (Scheme 57,llBOM2666). 

Nitriles. Nitriles can be prepared by a number of methods, including ( /) the reaction of alkyl haHdes with alkaH metal cyanides, (2) addition of hydrogen cyanide to a carbon—carbon, carbon—oxygen, or carbon—nitrogen multiple bond, (2) reaction of hydrogen cyanide with a carboxyHc acid over a dehydration catalyst, and (4) ammoxidation of hydrocarbons containing an activated methyl group. For reviews on the preparation of nitriles see references 14 and 15. 

Alternative paths for decomposition of the metal carboxylate can lead to ketones, acid anhydrides, esters, acid fluorides (1,11,22,68,77,78), and various coupling products (21,77,78), and aspects of these reactions have been reviewed (1,11). Competition from these routes is often substantial when thermal decomposition is carried out in the absence of a solvent (Section III,D), and their formation is attributable to homolytic pathways (11,21,77,78). Other alternative paths are reductive elimination rather than metal-carbon bond formation [Eq. (36)] (Section III,B) and formation of metal-oxygen rather than metal-carbon bonded compounds [e.g., Eqs. (107) (119) and (108) (120). Reactions (36) and (108) are reversible, and C02 activation (116) is involved in the reverse reactions (48,120). 

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