Cleavage mechanisms agents

Active Raney nickel induces desulfurization of many sulfur-containing heterocycles thiazoles are fairly labile toward this ring cleavage agent. The reaction occurs apparently by two competing mechanisms (481) in the first, favored by alkaline conditions, ring fission occurs before desul-, furization, whereas in the second, favored by the use of neutral catalyst, the initial desulfurization is followed by fission of a C-N bond and formation of carbonyl derivatives by hydrolysis (Scheme 95). 

The cleavage of the isoxazole ring by organomagnesium compounds may proceed by either one or both of two alternative mechanisms. Magnesium subhalides produced during the associated reaction may act as reducing agents as proved in specific cases.Another possibility is that the reduction involves a six-membered cyclic complex (171). 

Arya DP (2006) Diazo and Diazonium DNA Cleavage Agents Studies on Model Systems and Natural Product Mechanisms of Action. 2 129-152 El Ashry ESH, El KUany Y, Nahas NM (2007) Manipulation of Carbohydrate Carbon Atoms for the Synthesis of Heterocycles. 7 1-30 El Ashry ESH, see El Nemr A (2007) 7 249-285... 

The initially proposed mechanism [14], and one that continues to be considered as the likely pathway for most variants, involves the oxidative cyclization of a Ni(0) complex of an aldehyde and alkyne to a metallacycle (Scheme 18). Metallacycle formation could proceed independently of the reducing agent via metallacycle 19, or alternatively, metallacycle 20a or 20b could be formed via promotion of the oxidative cyclization transformation by the reducing agent. Cleavage of the nickel-oxygen bond in a o-bond metathesis process generates an alkenyl nickel intermediate 21. In the variants involv-... 

This approach was the first application of non-enediyne carbon centered radical mediated DNA cleavage agents that were not only capable of binding to DNA but could also be sequence specific. Further work is still needed to elucidate and confirm the sites of cleavage, nature of binding of these molecules and the mechanism of hydrogen abstraction from the nucleic acid backbone. 

While the successful DNA cleavage with copper(II)acetate establishes the mediacy of a similar activation mechanism with kinamycins, as shown before with 9-diazofluorenes, their mode of action may or may not involve the use of an oxidizing agent under physiological conditions. An important cor-... 

Arya DP (2006) Diazo and Diazonium DNA Cleavage Agents Studies on Model Systems and Natural Product Mechanisms of Action. 2 129-152... 

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