Anodic Oxidation of Nitrogen-Containing Compounds

Finally, it is important to note that many of the anodic reactions discussed above cannot be duplicated with traditional chemical oxidants. For this reason, the anodic oxidation of nitrogen-containing compounds represents a powerful class of reactions that has the potential to open up entirely new synthetic pathways to complex molecules. From the work already accomplished, it is clear that employing such an approach is both feasible and beneficial, and that the ability to selectively oxidize amines and amides is a valuable tool for any synthetic chemist to have at their disposal. 

Anodic Oxidation of Nitrogen-Containing Compounds VII. AMINO ALCOHOLS AND AMINO ACIDS... 

Nitrogen compounds are also effective as nucleophiles in the anodic oxidation of silyl-substituted ethers. The electrochemical oxidation in the presence of a carbamate or a sulfonamide in dry THF or dichloromethane results in the selective cleavage of the C-Si bond and the introduction of the nitrogen nucleophile at the carbon (Scheme 21) [55]. Since a-methoxycarbamates are useful intermediates in the synthesis of nitrogen-containing compounds [44], this reaction provides useful access to such compounds. Cyclic silyl-substkuted ethers such as 2-silyltetrahydrofurans are also effective for the introduction of nitrogen nucleophiles. The anodic oxidation in the presence of a carbamate or a... 

Nitrogen-containing compounds having lone-pair electrons are usually relatively easy to oxidize. Therefore the anodic behavior of such compounds has been studied quite intensively. However, the ease of oxidation is not always paralleled by the selectivity of the... 

Compounds containing the C=N functional group derivatives undergo anodic oxidation when the nitrogen atom bears an electron-rich heteroatom. Perhaps the simplest such species are aldoximes, which are anodically oxidized to nitrile oxides (34)38. The reaction was carried out in an undivided cell3 , hence the species 34 underwent immediate reduction to a nitrile (equation 19). However, since nitrile oxides are 1,3-dipolar species, one could in principle carry out the oxidation in a divided cell in the presence of a good 1,3-dipolarophile40 to effect the synthesis of substituted heterocycles. 

ICPs can be prepared from a large number of organic monomers by chemical or electrochemical methods. Both approaches involve the oxidation of the educt by using either appropriate oxidants or the anode in an electrochemical cell. Except for pofy-acetylene, all monomers and their respective polymeric oxidation products contain heteroatoms like o grgen, nitrogen, and sulfur. Those monomers, which can be electropotymerized, always contain heteroatoms. A selection of parent compounds is depicted in Figure 2. 

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