Halide-directed nitrile hydrolysis

Electrochemical Synthesis of the Aryl α‐Ketoesters from Acetophenones Mediated by KI

“…Over the past several decades, chemists have paid great attention to the synthesis of α‐ketoesters. Classical methods include oxidation of α‐hydroxy esters with various kinds of oxidant,4 oxidation of methyl 2‐phenylacetate,5 Friedel–Crafts acylation,6 hydrolysis and esterification of acyl cyanides,7 hydrolysis of 2‐aryl‐2‐nitroacetates,8 and other methods 9. However, these protocols usually require stoichiometric amounts of metal oxidants, and thus a large amount of waste is formed in the reaction.…”

Synthesis, crystal structure and herbicidal activity of mimics of intermediates of the KARI reaction

“…The ethyl 3‐hydroxy‐2‐oxo‐(substituted)‐butanoate products can be synthesized by bromination and hydrolysis of the corresponding α‐keto esters. Several methods reported for the synthesis of α‐keto esters are based on the alcoholysis of acyl cyanides,14 the addition of alkyl lithium reagents to triethoxyacetonitrile15 and the peracid oxidation of diazoesters 16. Weinstock et al 13 reported a one‐pot synthesis of α‐keto esters using diethyl oxalate and Grignard reagent.…”

An Efficient and Metal–free Synthesis of α‐Ketoesters via Oxidative Cross Coupling of Arylglyoxals with Alcohols

“…Besides this, they have been employed as synthetic precursors for a variety of organic transformations . α‐Ketoesters are also used as crucial intermediates for the synthesis of bioactive compounds such as inhibitors of proteolytic enzymes, inhibitors of leukotriene A4 hydrolase and photopolymerization initiators . Hence, several methods have been developed for their synthesis.…”

“…[2] a-Ketoesters are also used as crucial intermediates for the synthesis of bioactive compounds such as inhibitors of proteolytic enzymes, [3] inhibitors of leukotriene A4 hydrolase [4] and photopolymerization initiators. [5] Hence, several methods have been developed for their synthesis.Traditional methods for the synthesis of a-ketoesters involve the chemoselective cross-coupling reaction of monoesters of dicarboxylic acid chlorides with organocopper reagents derived from Grignard reagents, CuBr and LiBr, [6] oxidation of a-hydroxy esters with either CrO 3 in pyridine [7a] or Dess-Martin periodinane, [7b] Friedel-Crafts acylation of aromatic compounds with alkyl oxalyl chlorides, [8] oxidative cleavage of cyano keto phosphoranes with ozone to form a,b-diketonitriles followed by their in situ reaction with alcohols, [9] hydrolysis and esterification of acyl cyanides, [5] reaction of dialkyl oxalate with aryllithium in a flow microreactor, [10] aerobic oxidation of a-aryl halogen esters, [11] copper catalyzed aerobic oxidative esterification of 1,3-diones [12] and acetophenones [13] with alcohols,…”

“…Traditional methods for the synthesis of a-ketoesters involve the chemoselective cross-coupling reaction of monoesters of dicarboxylic acid chlorides with organocopper reagents derived from Grignard reagents, CuBr and LiBr, [6] oxidation of a-hydroxy esters with either CrO 3 in pyridine [7a] or Dess-Martin periodinane, [7b] Friedel-Crafts acylation of aromatic compounds with alkyl oxalyl chlorides, [8] oxidative cleavage of cyano keto phosphoranes with ozone to form a,b-diketonitriles followed by their in situ reaction with alcohols, [9] hydrolysis and esterification of acyl cyanides, [5] reaction of dialkyl oxalate with aryllithium in a flow microreactor, [10] aerobic oxidation of a-aryl halogen esters, [11] copper catalyzed aerobic oxidative esterification of 1,3-diones [12] and acetophenones [13] with alcohols, copper-catalyzed aerobic oxidative dehydrogenative coupling of a-carbonyl aldehydes with alcohols. [14] In addition, Smonou et al [15] prepared a-ketoesters via oxidative cleavage of bketoesters by using a combination of Oxone and AlCl 3 in water whereas, Tanaka et al [16a] and Yamamoto et al [16b] synthesized aketoesters via palladium-catalyzed double carbonylation of aryl halides with alcohols in the presence of NEt 3 .…”