Reductive alkylation, of cyanoacetic

A clean twofold Heck coupling of unsubstituted butadiene 46 (R = H) in the 1- and 4-positions has not been reported. However, the initial carbopalladation product from 46 (R = H) and an in situ formed arylpalladium halide, the cr-allylpalladium halide 47 equilibrating with the corresponding 7r-allylpalladium halide, can efficiently be trapped with the anion formed by arylation of malononitrile or cyanoacetate to give 48, a product of reductive 1,4-arylation-alkylation of 1,3-butadiene 46 (R = H)." /3-Hydride elimination from the intermediate 47 (R H) can be accomplished when the reaction is carried out in the presence of silver acetate or thallium acetate, leading to the... 

A re-investigation of the reaction between diketen and amides has shown that N-acetoacetylcarboxamides are formed most efficiently in the presence of trimethylsilyliodide. Olefins react with primary amides in the presence of mercury(ii) nitrate to give iV-substituted amides after NaBH4 reduction. The method provides a convenient procedure for the Markovnikov amidation of double bonds yields vary from 17 to 99% over 11 examples. Direct C-alkylation of secondary thioamides is achieved by the reaction of the dianion (177) with an activated halide to give (178). Esters of malonic, cyanoacetic, and /8-keto acids are readily C-amidoethylated by N-acylaziridines in the presence of triethylamine. ... 

Catalytic reduction of the 2-nitrophenyIhydrazones (745) and subsequent air oxidation of the tetrahydro-l,2,4-benzotriazines (746) which are formed is used for the synthesis of 3,4-dihydro-1,2,4-benzotriazines (747) (80FES715). In another cyclization of an o-nitro group, which somewhat resembles others (e.g. 736 —> 737) described earlier, treatment of l,l-dialkyl-2-(2-nitrophenyl)hydrazines (748) with acids affords 2-alkyl-1,2,4-benzotriazinium salts (749) (77JCS(P1)478). The 2-nitrophenylbromohydrazone (750) with sodium ethoxide and ethyl cyanoacetate forms 6-bromo-3-phenyl-l,2,4-benzotriazine (751) a mechanism for this interesting transformation, in which the cyanoacetate plays no part, has been proposed (79JHC33). 

The condensation of an aldehyde with ethyl cyanoacetate and ammonia to give 4-alkyl-3,5-dicyano-6-hydroxy-2-pyridone (XIl-198) probably proceeds through the oxidation of an intermediate glutaric acid imide -197). Only small amounts of the reduction products (XI-199)could be isolated. Additional pathways for the oxidation of W-197 to XII-198 were not excluded. ... 

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