Aminocyclopropanecarboxylate

Aminocyclopropanecarboxylic acid an a ammo acid that is the biological precursor to ethylene in plants... 

Scheme 11.35. Preparation of various protected substituted 1-aminocyclopropanecarboxylic acid (ACC) derivatives 138-R from N,N-dibenzylamino(benzyloxymethyl)cyclopropanes 133-R [109,110],...

The asymmetric syntheses of carnosadine (lS,2S)-74 [101] and of its protected derivatives as conformationally constrained surrogates for arginine have also been reported [102]. Different 2-substituted 1-aminocyclopropanecarboxylic acids have also been prepared by azidation of optically active 2-chloro-2-cyclo-propylideneacetates [103] and from the cyclopropanation of chiral bicyclic lactams [104]. 

Selectively deuterated 1-aminocyclopropanecarboxylic acid ACC 71 was prepared to investigate the biosynthesis of ethylene in plants [105 a] and of ammonia and 2-ketobutyrate in Pseudomonas [105bj. 

Aminocyclopropanecarboxylic acid-metal complexes 79 (M = transition metal with tetracoordination) also provide useful plant growth regulators, Eq. (30) [110]. 

The a-azidoesters 197-Me are not only precursors for a,)3-diamino acids 198 but could also be used to prepare 2 -substituted aminocyclopropanecarboxylic acid (ACC) derivatives 203 [10b, c, 62] (Scheme 60). Upon treatment with freshly prepared lithium methoxide in THF and subsequent hydrolysis (HCI), the a-... 

Achiral cycloalkyl quaternary amino acids have also been incorporated into model peptides using 5(47/)-oxazoIones as intermediates. A comparative study between cyclic and acyclic derivatives has been described. The influence of the ring size of a homologous series from l-aminocyclopropanecarboxylic acid to... 

The reaction of diazomethane with 2-phenyM-(sulfanylmethylene)-5(4//)-oxazolone 665, readily obtained from 4-(chloromethylene)-2-phenyl-5(4//)-oxazo-lone 394, generates the intermediate spirocyclopropane oxazolones 666 and 667, respectively. Both 666 and 667 were independently elaborated to the 2-sulfanyl-1-aminocyclopropanecarboxylic acid derivatives 668 and 669—a novel class of conformationaUy constrained masked cysteines (Scheme 7.210). Representative examples of spirocyclopropane oxazolones are shown in Table 7.47 (Fig. 7.58). 

Diphenyldiazomethane has also been used in 1,3-dipolar cycloadditions with 4-arylmethylene-5(47/)-oxazolones 670 to prepare gem-diphenyl-spirocyclopropane oxazolones 671." A number of 671 analogues were evaluated as antibacterial agents. " In addition, 671 derivatives were precursors for new 1-aminocyclopropanecarboxylic acid derivatives 672, for example, l-(benzoylamino)triphenylcy-clopropanecarboxylic acid 672 (R = Ar = Ph) (Scheme 7.211). 

The unusual amino acid, 1-aminocyclopropanecarboxylic acid, a precursor of the phytohormone ethylene, is biosynthesized in plants from S-adenosylmethionine. By using dideuterated S-adenosylmethionine, the reaction, under the influence of a pyridoxal phosphate dependent synthase, involves an inversion at the x-carbon center (a feature rarely observed for pyridoxal phosphate reactions), leading to (5)-l-amino-2,2-dideuterocyclopropanecarboxylic acid4. 

Cyclization. A second kind of reaction is represented by the conversion of S-adenosylmethionine to aminocyclopropanecarboxylic acid, a precursor to the plant hormone ethylene (see Chapter 24).159 The quinonoid intermediate cyclizes with elimination of methylthioadenosine to give a Schiff base of the product (Eq. 14-27).160-161a The cyclization step appears to be a simple SN2-like reaction.162... 

FIGUR E19. Bond lengths (A) and bond angles (deg) in 1-aminocyclopropanecarboxylic add (74). Mean values are shown as calculated from the reported data133... 

The preference for conjugate addition exhibited by a,/J-unsaturated acylphosphoranes even toward the addition of such hard nucleophiles as alkyllithiums is exploited for the preparation of 2-alkylcyclopropylacyl compounds from y-halogenated acylphosphoranes and alkyllithiums (equation 30). 1-Aminocyclopropanecarboxylic acid derivatives have... 

Beumer R, Bubert C et al (2000) The synthesis of diastereo- and enantiomerically pure P-aminocyclopropanecarboxylic acids. J Org Chem 65 8960-8969... 

But chrysanthemic acid derivatives are by far not the only examples of cyclopropane-containing structures in nature. In fact, the highly strained three-membered carbocycle is virtually ubiquitous. It occurs, for example, in every green plant in the form of 1-aminocyclopropanecarboxylic acid (ACC) 2, a direct precursor to the plant hormone ethylene [3]. In addition, the cyclopropane unit is found in a variety of other natural products, inter alia in terpenes and in various cyclopropanated fatty acids [4]. The biochemical precursors of the latter are unsaturated fatty acids, and in view of the existence of polyunsaturated fatty... 

Aminocyclopropanecarboxylic acid (74) has attracted special interest (a) as a modified model of natural a-amino acids, in the synthesis of bioactive peptide analogs, potential enzyme inhibitors , or e.g. a derivative with sweetness receptor activity s and (b) together with its Schiff-base metal complexesas the biosynthetic precursor of ethene, the plant ripening hormone . (See these sources and the review in Reference 135 for further references.)... 

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