Synthese der 1-aminocyclopropan-1-carbonsäure

Natural Occurrence, Syntheses, and Applications of Cyclopropyl-Group-Containing α-Amino Acids. 1. 1-Aminocyclopropanecarboxylic Acid and Other 2,3-Methanoamino Acids

“…84 During the course of investigations directed at developing novel syntheses of fluoroamino acids, fluorodehydroxylation of 2-methylserine afforded not only the expected 2-(fluoromethyl)alanine in 18% yield but also the undesired 1-aminocyclopropanecarboxylic acid hydrochloride in 28% yield. 85 An early discovered synthetic route, valuable until today, is the "diazo addition method", [86][87][88][89][90][91][92][93] in which diazomethane is added to a 2-aminoacrylic acid derivative 15, forming a pyrazoline 16, which can be fragmented thermally with liberation of nitrogen to form the amino acid derivative 19. This method has been extended to a highly efficient, small scale synthesis of ACC with virtually 100% overall yield (Scheme 2).…”

“…An early discovered synthetic route, valuable until today, is the “diazo addition method”, − in which diazomethane is added to a 2-aminoacrylic acid derivative 15 , forming a pyrazoline 16 , which can be fragmented thermally with liberation of nitrogen to form the amino acid derivative 19 . This method has been extended to a highly efficient, small scale synthesis of ACC with virtually 100% overall yield (Scheme ). , An essentially analogous transformation has been performed using oxosulfonium ylides as the cyclopropanating agents …”

“…This method has been extended to a highly efficient, small scale synthesis of ACC with virtually 100% overall yield (Scheme ). , An essentially analogous transformation has been performed using oxosulfonium ylides as the cyclopropanating agents 2 Commonly Used Syntheses of Protected ACC Derivatives: The “Diazo Addition Method”, − Cyclodialkylation of Dialkyl Malonates with Subsequent Conversion of One Ester Group, − Cyclodialkylation of Enolizable Glycine Equivalents 60,61,99-110 and γ-Dehydrobromination of α-Amino-γ-bromobutyric Acid Derivatives 111-115 …”

Synthesis and properties of 1-aminocyclopropane-1,2-dicarboxylic acid and compounds incorporating it

“…50 Spirocyclopropene 28 obtained by addition of diazoindene to dimethyl acetylenedicarboxylate (17) with subsequent elimination of a nitrogen molecule and cyclisation of the vinylcarbenium intermediate 29 reacts with 2-diazopropane to give a spiro derivative 30. 51 The reaction of substituted spirocyclopropenefluorenes 31 with 1-(3,5-dinitrophenyl)-3,4-dihydroisoquinoline (32) in anhydrous diethyl ether was studied. 52 In addition to the expected products (tetrahydroindolizines 33), this reaction gave novel spiroazanorcarenefluorenes 34 formed upon intramolecular 1,6cyclisation of the intermediate 35 (Scheme 1).…”

Methyl 2-acetylaminoacrylate in the reaction with aliphatic dienes

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Cycloaddition reactions (Huisgen reaction, DielsAlder reaction) of diazo compounds and dienes with dehydroamino acids derivatives (dehydroalanine, dehydrophenylalanine) are a convenient method for the synthesis of functionalized ring systems like pyrazolines [1], pyrazoles [2], cyclopropanes [3,4], norbornenes [5,6], and 9,10-ethanoanthracenes [7]. The interest in these carbo-and heterocycles representa-tives is due to the possibility of their use as precursors for the synthesis of cyclic α-amino acids, which are promising in terms of their structural and biological properties [8-10].

We first carried out the reaction of methyl 2-acetylaminoacrylate I with aliphatic dienes, the 2,3-dimethylbutadiene and isoprene.

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