1 - Aminocyclopropane-1 -carboxylate

ACCS Aminocyclopropane carboxylic FIIA How injection immunoassay... 

This version of the Curtius rearrangement has been applied to the synthesis of amino acid analogs and structures containing amino acids. Several m-2-aminocyclopropane carboxylate esters were prepared by selective hydrolysis of cyclopropane-1,2-dicarboxylates, followed by reaction with DPPA.267... 

PLP-dependent enzymes catalyze the following types of reactions (1) loss of the ce-hydrogen as a proton, resulting in racemization (example alanine racemase), cyclization (example aminocyclopropane carboxylate synthase), or j8-elimation/replacement (example serine dehydratase) (2) loss of the a-carboxylate as carbon dioxide (example glutamate decarboxylase) (3) removal/replacement of a group by aldol cleavage (example threonine aldolase and (4) action via ketimine intermediates (example selenocysteine lyase). 

Previously reported as a putative partial agonist at the glycineB-site (Fossom et al., 1995) 1-aminocyclopropane-carboxylic acid has more recently been shown to act as a glycineB-site agonist and concurrently as a glutamate-site antagonist (Nahum-Levy et al., 1999). 

Beumer, R. Reiser, O. /j-Aminocyclopropane-carboxylic acids with a-amino acid side chain functionality. Tetrahedron 2001, 57, 6497-6503. 

Photochemical Fe(CO)5-induced rearrangement of silylated allyl amine 9 gave N-silylated enamine 1015, which on subsequent Cu-catalyzed cyclopropanation by methyl diazoacetate afforded cyclopropane derivative 11. The use of an optically active catalyst gave an asymmetric induction of 56% ee for the cis isomer and 20% ee for the trans isomer. Further acid-induced ring cleavage afforded the -formyl ester 12, whereas reduction and desilylation produced aminocyclopropane carboxylic acid 13 (equation 2). 

Ethylene Chloroethyl phosphonic acid Aminocyclopropane carboxylic acid Aminoethoxivinyl glycine... 

It is not intended to list here all aminocyclopropane compounds with pharmacological or biochemical effects nor to mention the numerous papers dealing with investigations of the most outstanding aminocyclopropane derivatives such as tranylcypromine (see Section III.B.2) or aminocyclopropane carboxylic acid (see Section III.B.3). Biochemical aspects of aminocyclopropane derivatives are part of Chapter 16, which gives more comprehensive information. 

Aminocyclopropane carboxylic acid (6) has been detected in several plant tissues a procedure for preparing 6 from agricultural wastes, by extraction with a diluted solution of sulfosalicylic acid, has been described . 6 was established to be an intermediate product in ethylene biosynthesis " . Ethylene acts as a phytohormone which is involved in many metabolic processes in plants, e.g. in ripening, in stress situations or after wounding (see review and references cited therein). Natural 6 is formed from methionine via sulfonium salt (640) only S,S-(640) acted as a substrate for aminocyclopropanecarbo-xylate synthase, the S,R and R,R isomers of 640 were inactive as substrates . 6 can be... 

Aminocyclopropane carboxylic acid deaminase, obtained from Pseudomonas bacteria, decomposes 6 to ammonia and 2-ketobutyrate (647)3 i43.733-735 gy using R- and S-2,2-dideuterio-(6) it was shown that the methyl group in 647 has its specific origin in the pro-S methylene moiety of 63 ... 

Carnosadine (650), a guanidinomethyl aminocyclopropane carboxylic acid has been isolated from red algae G. carnosa. ... 

Aminocyclopropane- -carboxylic Acid. The acetyl derivative (170 mg) in H2O (2mL) and coned HCl (1 mL) was heated under reflux for 4 h. The mixture was evaporated to dryness under vacuum, the crystalline residue dissolved in H2O, and passed down an anion exchange column (IR-4B, 10 g, 20-50 mesh). Evaporation of the eluate in vacuo gave 1-aminocyclopropane-l-carboxylic acid as colorless crystals yield 87 mg (73%) mp 299-231 °C (HjO/EtOH). 

However, when these experiments were repeated with deuterated 1-aminocyclopropane-carboxylic acid, the resulting ethene showed retention of configuration, in contrast to the oxidation by transition metals (vide supra) ... 

The monoester 2 was converted by standard methods into the cyclopropene equivalent of aminocyclopropane carboxylic acid." The cyclopropene is a time-dependent inhibitor of ethenc biosynthesis and an extremely poor substrate for acetylene produetion and a preventative of senescence. 

In a detailed study of the malonyltransferases from peanut, four distinct malonyltransferase enzymes with different substrate specificities were Isolated from seedling hypocotyls and leaves (119). These four malonyl transferase enzymes had very distinct substrate specificity requirements, and except for one of these enzymes, no overlap in substrate specificity was observed. The four malonyltransferases were active with the following substrates (a) 3,5-dlchloroanlllne, (b) anthranilic acid, (c) 2-methoxyethanol, and (d) D-tryptophan and aminocyclopropane carboxylic acid. The malonyltransferase from peanut leaves and hypocotyls that utilized 3,5-di-chloroaniline as a substrate is probably similar to the transferase from peanut cell culture that utilized aniline as a substrate. 

In this last section the preparation of aminocyclopropane carboxylic acid derivatives by nitrogen extrusion from cyclic azoalkanes will be discussed. These amino... 

The second chirality source used in the synthesis of aminocyclopropane carboxylic acids was D-glyceraldehyde acetonide, which after Wittig-Homer-Emmons reaction provided the alkenes 61. Treatment with diazomethane and subsequent irradiation at low temperatures alforded the cyclopropanes 62, which were converted into several other derivatives by modification of the side chain (Scheme 11). Notably, the best results were obtained by irradiating in the presence of benzophenone as triplet sensitizer [33, 34]. Following a similar synthetic procedure allocoronamic acid 65 was prepared, which is one of the amino acids that can be processed by plant tissues and promises the possibility to control the enzymatic processes underlying plant growth and fruit ripening [35]. 

Rupp, L.A., DeVries, H.E., Mudge, K.W., 1989a. Effect of aminocyclopropane carboxylic acid and aminoethox-ivinylglycine on ethylene production by ectomycorrhizal fungi. Can. J. Bot. 67, 483-485. 

The copper (I) catalyzed cyclopropanation of amino acid protected pyrroles 37 with methyl diazoacetate proceeds smoothly to afford exclusively the exo-isomers 38 and 39, which were utilized as precursors to conformationally restricted peptides having a aminocyclopropane carboxylic acid <97SL202>. 

L-Methionine, (S)- -amino-y-methylthiobutyric acid, is one of the most important sulfur-containing primary amino acids. Secondary products derived from L-methionine either contain still the more or less complete methionine skeleton [cf. the formulas of S-adenosyl-L-methionine, azetidine-2-carboxylic acid, 1-aminocyclopropane carboxylic acid (Fig. 192), spermidine and spermine (Fig. 193)], or only the methyl group of L-methionine (most 0-, iV-, S- and C-methylated secondary products). The sulfur-containing derivatives possess either a sulfide (—S—) or a sulfonium (—S+—) group. 

Fig. 12 Observed conformers for 1-aminocyclopropane carboxylic acid (Ac3c). (From [112])...

Interestingly, cyclopropanone hemiacetals provide a rapid way to prepare a-aminocyclopropane-carboxylic acids (ACCs) and phosphonic acids analogues (ACPs). Thus, asymmetric Strecker reaction of hemiacetal with an amine in acidic sodium cyanide selectively affords ci5 -a-aminocyclopropane-carbonitriles, precursors of ACC amino acid derivatives (eq 24). ... 

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