1 -Aminocyclopropanecarboxylic acid

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 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. 

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... 

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.)... 

FIGURE 19. Bond lengths (A) and bond angles (deg) in 1-aminocyclopropanecarboxylic acid (74). Mean values are shown as calculated from the reported data ... 

The ylide from racemic (diethylamino)(methyl)(oxo)(phenyl)sulfonium tetrafluoroborate has been used to prepare cyclopropane derivatives required in the synthesis of several naturally occurring 1-aminocyclopropanecarboxylic acids. High diastereoselectivity combined with high yields (from optically active substrates) make this procedure attractive for cyclopropana-tion of alkenes. 

Analogously, 1-aminocyclopropanecarboxylic acid (20) was prepared from cyclopropane-1,2-biscarboxamide (18) via spirohydantoin 19 in good yield. ... 

Diazotization of cyclopropylamines in the presence of a chloride source is also a useful method for the preparation of some chlorocyclopropanes. When 1-aminocyclopropanecarboxylic acid was treated with nitrous acid in the presence of potassium chloride, 1-chlorocyclopropanecarb-oxylic acid (9) was isolated in 75% yield. Similarly, a modified Sandmeyer reaction of 7-ami-nocyclopropanoacenaphthylene (10) yielded 7-chlorocyclopropanoacenaphthylene (11). ... 

Diazotization of 1-aminocyclopropanecarboxylic acid with nitrous acid in the presence of lithium bromide gave 1-bromocyclopropanecarboxylic acid (16) in 75% yield. ... 

Diazotization of 1-aminocyclopropanecarboxylic acid in the presence of ethanethioic S-acid proceeded uneventfully and gave l-(sulfanylacetoxy)cyclopropanecarboxylic acid in 60% isolated yield.C—Si bond cleavage took place when cyclopropyltrimethylsilane and trimethyl-silyl chlorosulfonate were refluxed in cyclohexane giving trimethylsilylcyclopropanesulfonate in 70% yield. 

Diazotization of 1-aminocyclopropanecarboxylic acid in the presence of a carbon nucleophile gives a-substituted cyclopropanecarboxylic acids in moderate yields. When this amino acid was allowed to react with sodium nitrite in trifluoroacetic acid or with nitrosyl tetrafluoroborate in acetonitrile in the presence of potassium cyanide, 1-cyanocyclo-propanecarboxylic acid (1) was obtained in 64% yield. Similarly, l-(3-trimethylsilylprop-yl)cyclopropanecarboxyIic acid (2) was isolated in 30% yield when diazotization was carried out in the presence of allyl trimethylsilane. ... 

Treatment of an aqueous solution of the cobalt(III) bis(ethylenediamine) complex of 1-aminocyclopropanecarboxylate 1 with ammonium sulfide followed by hydrochloric acid gave cobalt(II) sulfide and the hydrochloride salt of 1-aminocyclopropanecarboxylic acid (2). ... 

The palladium-catalyzed hydrogenolysis of 1-aminocyclopropanecarboxylic acid (18, R = H) and its methyl ester led to the cleavage of two different cyclopropyl bonds, depending on the reaction conditions.In water or methanol, fission of the proximal bond was favored, whereas in acetic acid the C2 —C3 bond was preferentially cleaved. This result was unexpected because protonation of the amino group should make this system similar to acceptor-substituted cyclo-... 

Usually, donor and acceptor functions are located at different ring carbon atoms, but there are also examples in which both functions are linked to the same atom. The most prominent compound of this type is 1-aminocyclopropanecarboxylic acid (ACC, 6), a naturally occurring amino acid which is the precursor of the fruit-ripening hormone ethene. In fruit tissues, such as apple tissue, this amino acid is oxidized to ethene, carbon dioxide and hydrogen cyanide by the enzyme ACC oxidase, also known as ethene-forming enzyme (EFE). This reaction has been studied in detail. ... 

Studies with deuterated and methylated derivatives of 6 have revealed that the generation of ethene is not a stereochemically controlled process. " The oxidation of deuterated 1-aminocyclopropanecarboxylic acid with transition metals such as copper(II) sulfate, sodium permanganate and potassium ferrate also proceeded without stereoselectivity. ... 

When 1-aminocyclopropanecarboxylic acid and analogs 7 were treated with lithium hypochlorite as oxidizing agent only small amounts of ethene were formed. The main products of this reaction were 3-hydroxypropanenitrile (8, X = OH Y = CN) and 3-hydroxypropan-amides 8 (X = OH Y = CONHR). ... 

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