Azodicarboxylic substituting addition

Alder, K., Pascher, F., Schmitz, A. Substituting additions. I. Addition of maleic anhydride and azodicarboxylic esters to singly unsaturated... 

Dimethyl azodicarboxylate mixed at room temp, with ethyl vinyl ether dimethyl 3-ethoxy-l,2-diazetidine-l,2-dicarboxylate. Y S6%. F. e., also in ether, s. J. Firl and S. Sommer, Tetrah. Let. 1969, 1133 mostly substituting addition (cf. Synth. Meth. 21, 349) s. ibid. 1137. 

Azodicarboxylic acid) substituting addition addition to enamine 20,502 suppl. 26... 

Azodicarboxylic acid ester adducts Hydrazines by substituting addition... 

In a similar manner the addition of ethyl azodicarboxylate to the morpholine enamine of cyclohexanone furnished the less substituted isomer (34) with the substituent in the axial orientation (2, 26). 

Scheme 6.80 Typical products obtained from the 64-catalyzed enantioselective addition of a-substituted (J-keto esters to di-tert-butyl azodicarboxylate (a-hydrazination).

Dimethyl azodicarboxylate (164) has been reported to undergo a [ 4 + 2] photocycloaddition to the diene (165) to give the 2,3-diazabicyclo[2.2.2]octene (166). An analogous solid-state addition has been described in the ox-azolone (167) to give the photodimer (IbS), and oxidation of the photoadduct derived from 1-oxoanhydromethylberberine and nitrosobenzene has been used in a synthesis of ring C-substituted benzo[c]phenanthridines. ... 

Mixed substituted orthoesters, e.g. (383 equation 180), can be obtained by addition of alcohols to ketene 0,0-acetals. With the aid of phosphoranes containing a ketene O,(7-acetal structure, various orthoesters, e.g. (384) and (385) (Scheme 70) were prepared. " Cyclic orthoesters (386)-(390) (Scheme 71) are formed in cycloaddition reactions of ketene 0,0-acetals with aldehydes, ketones, 7.848 gj.yj cyanides, oxiranes, a-keto esters, o-diketones or ketones (with irradiation), a,3-unsaturated aldehydes and ketones (under pressure or catalyzed by ZnCh), diazoaceto-phenone, 7 diazoacetone and azodicarboxylate. ... 

Silylated (and germylated) hydrazines have been prepared by the addition of Ph3SiH, and similarly substituted silanes, to the N=N bond of diethyl and dimethyl azodicarboxylates. Spectroscopic data support formulations (5) and (6), and a radical mechanism could be substantiated for hydro-silylation whereas the addition of germanes proceeded via polar intermediates.72... 

Table 5. Bicyclo[2.1.0]pentane Derivatives via Addition of Dialkyl Azodicarboxylate or 4-Substituted-1,3,4-Triazole-3,5-dione to Cyclopentadienes...

P,P] Risaliti and co-workers in 1966 reported the stereoselective additions of enamines derived from cyclohexanone and morpholine, piperidine, and pyrrolidine to / -nitrostyrene (Eq. [1], Scheme 15) (34). The less-substituted enamines of the general structure 15.1 were isolated prior to hydrolysis. The location of the double bond of 15.1 was established by H-NMR spectroscopy and by addition to diethyl azodicarboxylate. The... 

New Diels-Alder adducts of thebaine with aromatic nitroso-compounds of structure (118 R = H, Me, Cl) have been prepared. These are unstable and can be hydrolysed to 14-aryIhydroxylaminocodeinones (119), which can be reduced to derivatives of the hitherto inaccessible 14-aminodihydrocodeinone (120). The base (119 R = H) is susceptible to base-catalysed displacement of the oxide bridge, the product being the 5,14-bridged thebainone derivative (121). ° The reaction between thebaine and excess of ethyl azodicarboxylate involves Diels-Alder addition and addition of the N-CH3 group to a second molecule of azo-ester. The primary product (122) has not been isolated pure, but yields ethyl hydrazodicarboxylate and the substituted codeinone (123) on hydrolysis. ... 

It is possible to trap the 2-substituted lithium derivatives produced by organometalUc addition with electrophiles for example the use of di-f-butyl azodicarboxylate leads, after a simple aerial oxidative re-aromatisation, to 2,5-disubstituted pyridines. ... 

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