Aminocyclopropanes

TABLE 10. Structural parameters of cyclopropylamine (121), 1-amino-1-methyl- (122) and 1 -amino- 1-phenylcyclopropane (123)  

A simultaneous crystallographic study (submitted for publication) ust a week later) gave essentially the same structure1 2 (Table 10). There are weak N—H- -N hydrogen bonds of N- -N 3.22 A in the crystal. 

TABLE 11. Structural parameters of cyclopropyl isocyanate (124) and isothiocyanate (125) and isocyanocyclopropane (126)  

The isocyano group has been found to be linear within 1° at the nitrogen atom in isocyanocyclopropane202 (126). The structure has been determined from the MW spectra with some assumptions (Table 11). There is little difference between distal and vicinal bonds the latter are slightly elongated compared to 1. 

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The reactions of dichlorocarbene with morpholine and piperidine enamines derived from cyclopentanone and cyclohexanone have been reported to lead to ring expanded and a-chloromethylene ketone products (355,356). Similarly a-chloro-a, -unsaturated aldehydes were obtained from aldehyde derived enamines (357). Synthesis of aminocyclopropanes (353,359) could be realized by the addition of diphenyldiazomethane (360) and the methylene iodide-zinc reagent to enamines (367). 

Aminocyclopropanes were prepared from enamines by the addition of Simmons-Smith reagent (688) or best through the cuprous-chloride-promoted decomposition of diazomethane (689). The reaction of an enamine with chloroform and base and opening of the resultant aminocyclopropane to an ynamine was reported (690). 

FACILE SYNTHESES OF AMINOCYCLOPROPANES N,N-DIBENZYL-iV-(2-ETHENYLCYCLOPROPYL)AMINE... 

Abbreviations ACC, 1-aminocyclopropane-l-carboxylic acid B, breaker stage... 

Belimov AA et al. (2001) Characterization of plant growth promoting rhizobacteria isolated from polluted soils and containing 1-aminocyclopropane-l-carboxylate deaminase. Can J Microbiol Al 642-652. 

Karthikeyan S, Q Zhou, Z Zhao, C-L Kao, Z Tao, H Robinson, H-w Liu, H Zhang (2004) Structural analysis of Pseudomonas 1-aminocyclopropane-l-carboxylate deaminase complexes insight into the mechanism of a unique pyridoxal-5 -phosphate dependent cyclopropane ring-opening reaction. Biochemistry 43 13328-13339. 

Walsh C, RA Pascal, M Johnston, R Raines, D Dikshit, A Krantz, M Houma (1981) Mechanistic studies on the pyridoxal phosphate enzyme 1-aminocyclopropane-l-carboxylate deaminase from Pseudomonas sp. Biochemistry 20 7509-7519. 

Glick BG, CB Jacobson, MML Schwarze, JJ Pasternak (1994) 1-Aminocyclopropane-l-carboxylic acid deaminase mutants of the plant growth promoting rhizobacterium Pseudomonas putida GR12-2 do not stimulate canola root elongation. Can J Microbiol 40 911-915. 

ACCS Aminocyclopropane carboxylic FIIA How injection immunoassay... 

Tomato Monsanto/1994 1 -Aminocyclopropane- l-carboxyUc acid deaminase (ACCD) Pseudomonas chloraphis Delayed softening due to reduced ethylene synthesis... 

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... 

Diacylmethylene)cyclopropanes (34) generated from the corresponding aminocyclopropanes 33 and acetylchloride (Scheme 6) are highly reactive intermediates and can be trapped by dienes such as 2,3-dimethylbutadiene (35), pentadiene 36 and isoprene (37) yielding the Diels-Alder products 38-40 [14]... 

Hot water treatment was reported to delay carotenoid synthesis and thus yellowing of broccoli florets (at 40°C for 60 min) and kale (at 45°C for 30 min), but did not affect Brussels sprouts (Wang 2000). Hot air treatment (38°C and 95% RH for 24 hr) slightly decreased lycopene and (3-carotene content in tomato fruit (Yahia and others 2007) however, fruit heated at 34°C for 24 hr and stored 20°C developed higher lycopene and (3-carotene than nonheated fruit (Soto-Zamora and others 2005). Moist (100% RH) hot air (48.5 or 50°C) for 4 hr caused injury to papaya and losses in lycopene and (3-carotene, but similar treatment with dry air (50% RH), alone or in combination with thiabendazole, had no effect on lycopene and (3-carotene (Perez-Carrillo and Yahia 2004). High-temperature treatment also suppressed 1-aminocyclopropane-l-carboxylic acid oxidase activity and thus indirectly prevented carotenoid synthesis (Suzuki and others 2005). 

Scheme 11.18. Aminocyclopropanation of the more highly substituted double bond in a conjugated diene a mechanistic rationalization [H6].

Versions of these aminocyclopropanations of terminal alkenes can also be applied intramolecularly. Terminally ethenyl-substituted N,N-dialkylcarboxamides such as 67 yield l-(dialkylamino)bicyclo[n.l.O]alkanes such as 68, while (w-alkenylamino)carboxa-mides such as 69 and 71 lead to 1 -alkyl-2-azabicyclo u.l.0]alkanes such as 70 and 72 (Scheme 11.20) [86,118], and N-allylamino acid N,N-dialkylamides furnish bicyclic diamines (see below). 

Scheme 11.21. Competition between aminocyclopropanation and hydroxycyclopropanation reactions [91,119],...

Scheme 11.33. Aminocyclopropanation of N-protected 2,5-dihydropyrroles 126 and debenzylation of the exo-6-amino-3-azabicyclo[3.1. OJhexane 129 [105b, 113].

The nonprotein amino acid, 1-aminocyclopropane-l-carboxylic acid, is an intermediate of ethylene biosynthesis in plants. This amino acid is synthesized from the L-a-amino acid methionine through the intermediate 5 -adenosyl-L-methionine (SAM) (Scheme 8). ... 

Aminocyclopropane-1-Carboxylate Synthase, an Enzyme of Ethylene Biosynthesis... 

The possibility that many organic compounds could potentially be precursors of ethylene was raised, but direct evidence that in apple fruit tissue ethylene derives only from carbons of methionine was provided by Lieberman and was confirmed for other plant species. The pathway of ethylene biosynthesis has been well characterized during the last three decades. The major breakthrough came from the work of Yang and Hoffman, who established 5-adenosyl-L-methionine (SAM) as the precursor of ethylene in higher plants. The key enzyme in ethylene biosynthesis 1-aminocyclopropane-l-carboxylate synthase (S-adenosyl-L-methionine methylthioadenosine lyase, EC 4.4.1.14 ACS) catalyzes the conversion of SAM to 1-aminocyclopropane-l-carboxylic acid (ACC) and then ACC is converted to ethylene by 1-aminocyclopropane-l-carboxylate oxidase (ACO) (Scheme 1). 

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