γ-Methylaminobutyraldehyde, a new intermediate in nicotine biosynthesis

Kisaki, Takuro; Mizusaki, Shigenobu; Tamaki, Einosuke

doi:10.1016/0003-9861(66)90111-1

Cited by 20 publications

(13 citation statements)

References 10 publications

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“…In an attempt to determine whether the three lower nicotine genotypes are characterized by low primary metabolic QPT activity, enzyme activity was determined in leaves of six-to eight-leaf plants grown under the standard conditions. Total QPT activity in the leaves was found to be low (mean 1.4 The role of putrescine, N-methylputrescine, and N-methyl-4-aminobutanal in the biosynthesis of the pyrrolidine ring of nicotine is supported by experiments involving isotope tracers (7,18), recovery and subsequent incorporation of labeled intermediate (13), isolation of enzymes and determination of substrate specificities (14,15), and tissue localization and response to decapitation (16). Our data showing that the levels of PMT and MPO are generally proportional to nicotine levels in these four closely related genotypes provides further supportive evidence for the nicotine biosynthetic scheme outlined by Mizusaki et al (15).…”

Section: Resultsmentioning

confidence: 99%

Nicotine Biosynthetic Enzyme Activities in Nicotiana tabacum L. Genotypes with Different Alkaloid Levels

Saunders¹,

Bush²

1979

Plant Physiol.

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Young plants of five Nicotiana tabacum L. genotypes were examined for activity of nicotine biosynthetic enzymes. Genotypes near isogenic except at two loci each with two alleles controlling nicotine level were used in a comparison of the four homozygous allelic combinations producing high, high intermediate, low intermediate, and low nicotine levels in a 'Burley 21" background. Putrescine N-methyltransferase (EC 2.1.1.53) and quinolinic acid phosphoribosyltransferase (EC 2.4.2.19) activities in root tissue of these four genotypes were proportional to leaf nicotine level, whereas N-methylputrescine oxidase activity in root tissue differed in proportion and ranking. Quinolinic acid phosphoribosyltransferase activities in leaf tissue were lower than in roots, but no differences were found among the four genotypes. The homozygous recessive alleles at either locus affect levels of all three enzyme activities examined in roots. Each locus seems to be involved in regulation of nicotine metabolism, but whether directly as a regulatory locus or indirectly through the metabolic product of a structural locus is not known.No difference was observed between enzymic oxidation of putrescine and N-methylputrescine by leaf and root extracts of Burley 21 (a high nicotine, low nornicotine genotype) and a high nornicotine cultivar, "Robinson Medium Broadleaf." Putrescine was utilized as a substrate to a greater extent than N-methylputrescine by leaf extracts compared with root extracts of both cultivars. It was concluded that genetic differences in levels of nicotine and nornicotine were not due to differences in enzymic oxidation of these two precursors during alkaloid biosynthesis.Nicotine is the predominant alkaloid in commercial tobacco cultivars, where it is found in concentrations of 2 to 5% of dry weight. Nicotine level as influenced by cultural practices of nitrogen fertilization, plant decapitation, water regime, and axillary bud control has been reviewed recently (2). Low total alkaloid levels are associated with homozygous recessive alleles at both the A and B genetic loci, and intermediate alkaloid levels are found when the homozygous recessive alleles are present at only one of the two loci (I 1).Nicotine, composed of single pyridine and N-methylpyrrolidine rings linked together, is synthesized primarily in the root (1,5). Support for the role of ornithine decarboxylase putrescine Nmethyltransferase (EC 2.1

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Section: Resultsmentioning

confidence: 99%

Nicotine Biosynthetic Enzyme Activities in Nicotiana tabacum L. Genotypes with Different Alkaloid Levels

Saunders¹,

Bush²

1979

Plant Physiol.

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“…The first total synthesis of the pyrrolidine–flavoalkaloids was achieved from 1,3,5-trimethoxybenzene in nine steps reported by Anjaneyulu and Govindachari. , The phloroglucinol moiety is present in most of the natural flavoalkaloids . Till date, no biosynthetic pathways have yet been reported, it is hypothesized that the N -methyl-pyrrolidinium ion formed from the amino acid, ornithine, is the precursor of N -methylpyrrolidine unit of isoficine, phylospadine, and ficine. , …”

Section: Introductionmentioning

confidence: 99%

Novel Cinnamoylated Flavoalkaloids Identified in Tea with Acetylcholinesterase Inhibition Effect

Gaur

Zhang

et al. 2020

J. Agric. Food Chem.

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3-O-Cinnamoylepicatechin (1) was synthesized along with four flavoalkaloids, (−)-6-(5‴S)-N-ethyl-2-pyrrolidinone-3-O-cinnamoylepicatechin (2), (−)-6-(5‴R)-N-ethyl-2-pyrrolidinone-3-O-cinnamoylepicatechin (3), (−)-8-(5‴S)-N-ethyl-2pyrrolidinone-3-O-cinnamoylepicatechin (4), and (−)-8-(5‴R)-N-ethyl-2-pyrrolidinone-3-O-cinnamoylepicatechin ( 5) via esterification of epicatechin followed by phenolic Mannich reaction of 1 with theanine in the presence of heat. The new compounds 1−5 were detected in leaves of three tea cultivars, Fuding-Dabai, Huangjingui, and Zimudan with the help of ultra-performance liquid chromatography hyphenated with a photodiode array detector and electrospray ionization high-resolution mass spectrometry (UPLC-PDA-ESI-HRMS), suggesting that they are naturally occurring in tea leaves. The structures of the novel natural products were characterized by one-and two-dimensional nuclear magnetic resonance (1D and 2D NMR) and mass spectroscopy. Compounds 1−5 were then evaluated for their acetylcholinesterase (AChE) inhibitory effect (IC 50 = 0.12−1.02 μM). The availability of the synthesized epicatechin derivatives 1−5 via a synthetic route enabled the first unequivocal identification of these derivatives as tea secondary metabolites and made it possible to determine their content in the tea material as well as the diverse bioactivities.

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“…The occurrence of y-methylaminobutyraldehyde as an effective prectursor of the nicotine hiosynthesis su,pports ouir previouis conclusion (12,20) that nicotine is synthesized throuigh a rouite( s) which does not involve nornicotine. Dawson and coworkers (4) have shown that the tritium la,beled oi-n C-6 of nicotinic acid was less eefficiently incor- …”

Section: Discussionmentioning

confidence: 99%

Phytochemical Studies on the Tobacco Alkaloids. XII. Identification of γ-Methylaminobutyraldehyde and its Precursor Role in Nicotine Biosynthesis

Mizusaki¹,

Kisaki²,

Tamaki³

1968

Plant Physiol.

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Abstract. y-Methylaminobutyraldehyde (N-methylpyrroline) labeled with 14C was isolated from tobacco roots which had metabolized ornithine-2-'4C. It was labeled most strongly 4 hours after adding ornithine-2-14C to the root, also labeled by putrescine-1,4-1 C and methionine-4CH,, and observed in the root but not in the aerial portions of tobacco plants. y-Methylaminobutyraldehyde when added back to the root was an efficient precursor of nicotine. Identity of y-methylaminobutyraldehyde from tobacco roots was confirmed by comparison with the authentic compound.The existence of y-methylaminobutyraldehyde (N-methylpyrroline) in the biosynthetic pathway of nicotine indicates that the methyl group must be introduced before condensation of the pyridine moiety with the pyrrolidine moiety.It has been Nvell establishedl that the pyridine ring of nicotine is derived from nicotinic acid (4), and the pyrrolid,ine ring from ornithine (7,16), pltitrescine (17), glutamic acid, and proline (14).'rhe mechanism of the condensation of the 2 rings was dliscuissed by Bverrum and hi.s grouip (15), Leete et al. (18), Dawson (5), and Mothes and Schtitte (21). Byerruim and his co-workers (2,6) demonstrated that the methyl group is introdui,ced f,rom methionine anid labile C1-fragments. However, intermediattes between these precuirsors and nicotine anid the mechaniism of the reaction have remained largely lunexI)lored.Ladesic and Tso (13) and Schroter (22) have reported that nornicotine canl serve as a precursor of nicotine. However, ouir previous paper (11) demonstrated that while nicotine always occulrs in the pulre i-form in tobacco plants, nornicotine isola,te(l from tobacco roots is predominantly d-form. We a,lso reported that radioactive nicotine and nornicotine isolated from sterile root cuiltuires of Nicotiaina, ritstica fed DL-ornithine-2-1 4C d-iffered in the di,strilbution of radioactivity between C-2 and C-5 in the pyrrolidine ring, and that only small amounts of 15N were incorporated into nicotiie by administra,tion of 15N-labeled nornicotiine (20). These findings led to the inference that the biosynthesis of nicotine occurs through a routte(s) that does not involve nornicotine. Alworth and I Present address:

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γ-Methylaminobutyraldehyde, a new intermediate in nicotine biosynthesis

Cited by 20 publications

References 10 publications

Nicotine Biosynthetic Enzyme Activities in Nicotiana tabacum L. Genotypes with Different Alkaloid Levels

Nicotine Biosynthetic Enzyme Activities in Nicotiana tabacum L. Genotypes with Different Alkaloid Levels

Novel Cinnamoylated Flavoalkaloids Identified in Tea with Acetylcholinesterase Inhibition Effect

Phytochemical Studies on the Tobacco Alkaloids. XII. Identification of γ-Methylaminobutyraldehyde and its Precursor Role in Nicotine Biosynthesis

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