Transfer and Related Reactions

The diazo transfer reaction, which involves the transposition of two nitrogen atoms from -toluenesulphonyl azide to a carbanion, wais first utilized by Doering and De Puy in the synthesis of diazocyclo-pentadiene (equation 138). The diazo transfer reaction has since 

Amine Azide (7o yield) Recovered T0SN3 (%) TosNH- (%) 

Although the mechanism of this reaction has yet to be fully established certain of its aspects have been defined. The intermediacy of the anion 269 is very probable, particularly since a solid which is presumably the intermediate (269 R = CgHs) has been isolated from the reaction of anilide ion with p-toluenesulphonyl azide. In support of the structural assignment this solid gave a mixture of phenyl azide (40%) and aniline when heated. The reaction sequence has been summarized as shown in equation (139). 

Anselme and co-workers have suggested that the stability of the 

Nitrous oxide (270) is related electronically to the azido group and has been examined as a potential dizizo transfer reagent. Meier  

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Roth, H. D. A Brief History of Photoinduced Electron Transfer and Related Reactions. 156, 1-20 (1990). 

Significance of the Br nsted Slope in Electron Transfer. Linear free energy relationships have been extensively studied for electron transfer and related reactions in both inorganic and organic systems. For highly endergonic reactions, the Br0nsted slope a is close to unity. In many cases, however, the more or... 

It is our purpose in his article to try and locate on the map the transition state for simple methyl transfers and related reactions with respect both to the symmetry, a, and to the tightness, r, of the transition state. We summarize here... 

A Brief History of Photoinduced Electron Transfer and Related Reactions... 

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