Reductions with diimide

Diimide (NH=NH) is a transient species generated by reaction of acids with potassium azodicarboxylate, 2 by thermolysis of anthracene-9,lO-diimine, fj-om hydrazine derivatives O qj- tosylhydrazone. Diimide 

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Namely, if the double bond was saturated ( ) simultaneously when it formed, the retardation of the development of conjugated polymer structure might be expected. We chose the reduction with diimide (NH=NH) for the saturation of double bond. Thus, p-toluenesulfonyl hydrazide (PSH) was used which acts as a diimide source under the condition (130-150°C) of PVC-processing. 

The procedure described is based on the selective reduction with diimide described by Ohno and Okamoto and by Nozaki and Noyori. It illustrates the generation of diimide from the air oxidation of hydrazine and the use of diimide for the selective reduction of the trans double bond in cis,trans,trans-, S,9-cyc o-dodecatriene, the product of trimerization of butadiene. ... 

Pd and Ni catalysts with the structural effects on reductions with diimide (diazene) (ref. 6) and the equilibrium constants for the association of substituted ethylenes with a Ni(0) complex (ref. 7). These particular reactions were chosen because of our perception of their relation to the mechanisms of catalytic hydrogenation, and the insightful analysis of the relationship between structure and reactivity provided by the authors of these studies. 

Table 1 Relative Reactivities of Substituted Alkenes Toward Reduction with Diimide ...

Table 2 Relative Reactivities of Unsaturated Acids Toward Reduction with Diimide " ...

The nitronate anion derived from nitro sugar 82, available from glucopyranoside 1 using standard methods, condenses with aldehyde 33 to afford adduct 83. Reduction with diimide of the ii-olefin, produced in low yield by radical elimination of the nitroaldol, and removal of the... 

Reviews. Hamersma and Snyder studied the effect of variation in reaction conditions in reductions with diimide generated from dipotassium azodicarboxylate. Air does not have a deleterious effect. Rate of reduction decreases with solvents in the following order pyridine > dioxane > dimethyl sulfoxide > methanol > ethanol > n-butanol, Water is a powerful inhibitor of the reaction in nonhydroxylic solvents but has practically no effect in hydroxylic solvents. 

Singlet oxygen adds readily to tetrahydrobenzopyrans (166) derived from the photoisomerization of j6-ionone <73ABC224i> and its derivatives, for example (167) <88JMC713>, to afford the corresponding trioxanes (168) and (169) (Equation (21)). The saturated derivatives are obtainable by reduction with diimide in the case of (165) and (169 and by hydrogenation over Pt for (168). 

Reduction with Diimide Daniel J. Pasto and Richard T. Taylor... 

Other methods of reduction 7.4.3 Reductions with diimide... 

Hydrazine oxygen copper ion Reductions with diimide s. 17, 22... 

Finally, mention must be made of the efforts of R. G. Salomon s group to synthesize several derivatives of 2,3-dioxabicyclo[2.2.1]heptane, the strained bicyclic peroxide nucleus of prostaglandin endoperoxide (206). They are prepared from 2,3-dioxabicyclo[2.2.1]hept-5-ene by selective reduction with diimide or chlorination. 

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