Nitrogen atom insertion

Direct Insertion. Nitrogen atom insertion. The phthalimidonitrene (163) formed by lead tetra-acetate oxidation of the corresponding hydrazine is reported to add to the carbon-carbon double bond of 2,5-disubstituted 

Brasen, and H. Miyake, Acta Chem. Scand., 1971, 25, 2055. 

Ichimura, Kobunshi Zairyo Kenkyusho Kenkyu Hokoku, 1969, 19, 1 Chem. Abs., 1972.76, 99 410). 

The nitrene (171), generated in a similar manner from the corresponding iV-amino-lactam, formed sulphoximide (e.g. 172) by addition to sulphoxides. The sulphoximide product on photolysis was found to regenerate the original sulphoxide and nitrene (171), which could be trapped with cyclohexene. Thermolysis of (172) again generated the nitrene (171), which under these 

Although the formation of aziridines from olefins and azides may not in all cases involve a nitrene intermediate, some recent literature reports of reactions of this type have for convenience been included in this section (see also the section on ring contraction). Alkoxycarbonyl nitrenes (R = Me or Et), 

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The more nitrogen atoms inserted in an aromatic nucleus, the more easily reducible the system becomes. When a heteroaromatic system has two (or more) nitrogen atoms in a six-membered ring, the compound is reducible, at least in acid solution, and if two nitrogen atoms occupy para positions in such a ring, the redox system approaches reversibility. 

Scheme 54 Nitrogen atom insertion into aryl C-H bond...

Of the various methods of inserting a nitrogen atom in the saturated alcohol, C10H22O (II), to form lupinine, the most probable are represented by formul (X) and (XI), of which the latter was preferred. 

Zollinger and coworkers (Nakazumi et al., 1983) therefore supposed that the diazonium ion and the crown ether are in a rapid equilibrium with two complexes as in Scheme 11-2. One of these is the charge-transfer complex (CT), whose stability is based on the interaction between the acceptor (ArNj) and donor components (Crown). The acceptor center of the diazonium ion is either the (3-nitrogen atom or the combined 7r-electron system of the aryl part and the diazonio group, while the donor centers are one or more of the ether oxygen atoms. The other partner in the equilibrium is the insertion complex (IC), as shown in structure 11.5. Scheme 11-2 is intended to leave the question open as to whether the CT and IC complexes are formed competitively or consecutively from the components. ... 

Most 1,3-diazepine syntheses employ the insertion of a single carbon fragment between the two nitrogen atoms. This is further exemplified by the use of tosyl isocyanate and methyl isothiocyanate in the preparation of the bicyclic imidazo[4,5-e][l,3]diazepines 46 and the imidazo[4,5-rf][l,3]diazepines 47 respectively <96JHC855, 96JCS(P1)2257>. 

Lim and Sulikowski (84) explored the intramolecular C-H insertion in 119 alpha to the nitrogen atom as a rapid entry to the mitomycin skeleton and the antitumor agent FR-900482. Rhodium(II) based catalysts provide nearly racemic products. Bis(oxazoline) (55b) affords highest selectivities in this system and chloroform was found to be the optimal solvent, Eq. 71. The authors note that the reaction is somewhat capricious. 

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