Alkaloids anabasine

The pyridine alkaloids anabasine (1), nicotine (2), ricinine (3), nomicotine (4) and trigonelline (5) form an important group of natural products. Thus anabasine (1) is extracted on a large scale in the Soviet Union (56MI20900) and functions as an insecticide with acute and subacute toxicity. Nicotine (2) has been used as an anthelmintic but more widely as an agricultural insecticide, functioning as a contact poison when combined with oleic acid... 

Determination of the configuration at the newly created stereogenic center in heterocycles 29a and 29b (obtained from imines 28a and 28b and the Danishefsky diene, p416) byconversion to the alkaloids ( -anabasine (31 a) and (S)-coniine (31b), respectively, through a reaction sequence involving removal of the auxiliary, as discussed on p 45613°,... 

The tobacco alkaloid anabasine (37) has been synthesized from 3-pyridyl-lithium (prepared from 3-bromopyridine and t-butyl-lithium) by reaction with A piperideine at —120 °C.46... 

The rather similar alkaloids anabasine and anatabine come from different biosynthetic pathways. Labelling experiments outlined below show the origin of one carbon atom from lysine and others from nicotinic acid. Suggest detailed pathways. (Hint. Nicotinic acid and the intermediate yoi have been using in Problem 3 in the biosynthesis of the piperidine alkaloid are both electrophilic at position 2. You also need an intermediate derived from nicotinic acid which is nucleophilic at position 3. The biosynthesis involves reduction.)... 

The well-known piperidine alkaloid anabasine, found in Anabasis aphylla L. (Chenopodiaceae) and Nicotiana glauca Graeb. (Solanaceae), is thought to be synthesized in plants through dimerization of A1-piperideine (followed by oxidation).243 A terpyridine nicotelline (173) was found in tobacco leaf,244andits structure was proved by synthesis.245... 

Miscellaneous alkaloids Anabasine Teratogenic, crooked calf disease 35U52... 

The alkaloids anabasine (86) and sedamine (87) are typical representatives of one such alkaloid family past results suggest that they are both formed by condensation of a suitable nucleophile with a unit of A piperideine (85) derived from lysine (Scheme 15). The nucleophile is possibly benzoylacetic acid for sedamine49 and has been shown to be derived from nicotinic acid for anabasine.50 The origin of the different side-chains will be discussed in detail later under the individual alkaloids. For the moment this account will focus on the pattern of incorporation of lysine and will try to correlate the results from different systems. 

Anabasine (3-pyridyl-2-piperidine) appears to be the sole constituent of N. glauca R. Grah., and this plant has been used for the study of the biogenesis of the alkaloid. Anabasine isolated from N. glauca cultured in hydroponic solution containing lysine-2-C hydrochloride is radioactive (53). The alkaloid when oxidized with nitric acid gives nicotinic acid which by decarboxylation yields pyridine and carbon dioxide isolated as barium carbonate. Whereas the activity of anabasine is... 

Although nicotine is the principal alkaloid in commercial tobaccos (Nicotiana tabacum and Nicotiana rusticd), norni-cotine is the main alkaloid in most other species of Nicotiana. Anabasine is the third most abundant tobacco alkaloid. Anabasine is found in the stem of the Nicotiana glauca plant. Anatabine has been reported as a minor alkaloid in the roots of these plants, although it is present also in the leaf and stem... 

Another compound, an alkaloid closely resembling the nicotine alkaloid anabasine, has been found in the Leguminosae, namely, ammo-dendrine, obtained from Ammodendron conollyi. 

Also obtained from tobacco are the alkaloids (-)-anabasine and (-)-anatabine and related derivatives. (-)-Anabasine is biosynthesized by combining nicotinic acid and a piperidine ring derived from lysine. 

In the tobacco alkaloids anabasine (26) and anatabine (27), a lysine derivative is condensed with a derivative of nicotinic acid to yield a system reminiscent of nicotine (Fig. 29.9) (Leete, 1977, 1983a). 

The alkylation of the alkaloid anabasin (XII-40S) with methyl iodide gives the hydroiodide of //-methylanabasin iodomethylate which gives A -dimethyl-anabasone (XII-406) when treated with potassium ferricyanide. ... 

Similar work was reported by Coldham and Leonori, who applied this methodology to the synthesis of the alkaloid anabasine [171b]. These workers used tBujP-HBF as the ligand. 

The pathways deduced for coniine 6.14) and pinidine 6.15) on the one hand, and anatabine 6.7) and dioscorine 6.8) on the other, are exceptional. That deduced for iV-methylpelletierine 6.19) can be considered much more typical of piperidine alkaloids because the piperidine ring originates from lysine 6.17). Two other alkaloids, anabasine 6.20) and sedamine 6.21) have similar origins and much of the evidence for the three alkaloids is interlocking so they are best discussed together. 

Nkotiana tabacum (tobacco) contains an alkaloid, anabasine, which is suspected teratogen in tobacco planb. Effects, include twisting and arthrogryposis, are likely in the offspring of sows that ingested stalks of the plant during the first trimester of gestation. 

DL-[2- H.6- C]lysine was incorporated into sedamine without loss of tritium, indicating an alternative pathway in plants from lysine to sedamine and other alkaloids. In this connection it is of interest that D-lysine is transformed into pipecolic acid whereas L-lysine is converted into the alkaloid anabasin in Nicotiana glauca. Analogously, in Pseudomonas putida, L-lysine is transformed into S-aminopentanoic acid but D-lysine into pipecolic acid. " The latter transformation has also been observed in corn and ryegrass seedlings. ... 

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