Diazo phenylacetate

Doyle and co-workers have recently reported Rh(ii) or copper complex-catalyzed reaction of aryldiazoacetate or vinyldiazoacetate with imines. " Diastereoselective aziridine formation is observed in the Rh2(OAc)4-catalyzed diazo decomposition of diazo phenylacetate in the presence of arylimine (Equation (28)). " When the reaction was carried out with aldehyde, epoxide 187 was obtained. 

Gonadotropin-Releasing Hormone-Azophenylacetic Acid (LH-RH Azophenylacetic Acid). LH-RH has blocked N and C terminals, and therefore a carboxyl group has to be introduced in order to make it available for conjugation to protein. This is performed by attaching p-diazo-phenylacetic acid to synthetic LH-RH, which results in the formation of an azo derivative. 

Silanes can react with acceptor-substituted carbene complexes to yield products resulting from Si-H bond insertion [695,1168-1171]. This reaction has not, however, been extensively used in organic synthesis. Transition metal-catalyzed decomposition of the 2-diazo-2-phenylacetic ester of pantolactone (3-hydroxy-4,4-dimethyltetrahydro-2-furanone) in the presence of dimethyl(phenyl)silane leads to the a-silylester with 80% de (67% yield [991]). Similarly, vinyldiazoacetic esters of pantolactone react with silanes in the presence of rhodium(II) acetate to yield a-silylesters with up to 70% de [956]. 

For the irradiation of methyl a-diazo-a-phenylacetate in styrene, the transjcis ratio of the resulting methyl 1,2-diphenylcyclopropane-l-carboxylate (6) was markedly diminished if the reaction was carried out in a frozen matrix rather than in liquid solution.This effect, which... 

Ethyl diazophenylacetate is reduced to phenylacetate in aqueous dioxane at pH 7 (Jugelt et al., 1972). The authors reported that dinitrogen is formed, clearly indicating that the mechanism of this reduction is different from that of 2-diazo-l-phenylethan-l-one. Under aprotic conditions (sulfolane), ethyl diazoacetate, but... 

Conversely, if the substituted phenylacetic acid or its chloride are not readily accessible, the diazo ketone obtained from the corresponding aromatic acid chloride and diazomethane may be treated directly with the substituted phenethylamine. An Arndt-Eistert type rearrangement occurs which leads directly to the phenethylamide of the respective homo acid. An example for this type of reaction may be found in the synthesis of 1-benzylhydrohydrastinine (61). 

An asymmetric N-H insertion reaction of methyl a-diazo-ot-phenylacetate (207) to B0CNH2 (208), catalysed by the dirhodium(II) complex and phosphoric acid (203) produced 2-(tert-butoxycarbonylamino)-2-aryl-acetate (209) in high yield and high enantioselectivity (Scheme 55). Asymmetric Fischer indolisation of 4-substituted cyclohexanone-derived phenylhydrazones (210) catalysed by spirocyclic chiral phosphoric acid (212-213) gave various 3-substituted tetrahydrocarbazoles (211) in high yields (Scheme 56). ... 

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