Carbon-nitrogen bonds oxidation synthesis

The synthesis of sodium channel inhibitor 1 [82] illustrates the utility of the /V-oxide strategy by using it not only to form the biaryl carbon-carbon bond, but also to form the C4 carbon-nitrogen bond. Diaryl ether 3, prepared by a copper catalyzed cross-coupling of 4-fluorophenol and l-bromo-4-iodobenzene [83], was coupled... 

Eight reactions involve carbon-nitrogen bond synthesis, in one a carbon-nitrogen bond is broken, and in only one case is a carbon-carbon bond formed. There are no oxidation-reduction reactions, and only one vitamin, folic acid, is involved. Four steps require ATP, but the first reaction uses PP-ribose-P as an equivalent energy donor. Four of the first five reactions are irreversible, whereas the last five are all reversible to some degree. 

Besides carbon-carbon and carbon-oxygen bonds, a successful carbon-nitrogen bond formation was also achieved utilizing a similar oxidative heterocyclization of enolizable ketones. An efficient synthesis of tetramic acids with a pyrrolidine-2,4-... 

The a-methoxylated derivatives are shown to be versatile synthons because of the reactivity of the methoxy group near the nitrogen atom, a-Methoxycarbamates, prepared by anodic oxidation, were used as key intermediates in the synthesis of a-amino acids,200 a new carbon-phosphorus bond-forming reaction,200 and in a new method of acylation of aliphatic amines at the -position.201 The application of this reaction to the synthesis of pyrrolidine, piperidine, and tropane alkaloids is also described.202... 

Matrix isolation methods of synthesis have also been used to prepare and study coordination compounds. These involve the vaporization of a metal and a potential ligand, which are then rapidly carried in a stream of inert gas to a very cold surface, where the compound which has been formed is quickly trapped in the solid matrix. It is possible to determine the type of bonding, the structure and the thermodynamic properties of the compounds formed. Only small ligand molecules have been used thus far carbon monoxide, nitric oxide, nitrogen and oxygen, for example, but molecules of great interest have been formed. Some such are [Pd(C2H4)], [Pd(N2)3], [Ni(N2)202], [Ni(N2)4] and [Ni(CO)(N2)3].41... 

Bryan, J. C., Mayer, J. M. Oxidative addition of carbon-oxygen and carbon-nitrogen double bonds to WCl2(PMePh2)4. Synthesis of tungsten metallaoxirane and tungsten oxo- and imido-alkylidene complexes. J. Am. Chem. Soc. 1990,112, 2298-2308. 

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