Alkaloids aconite

Abrine, 484 Abrotine, 772 Abrtis precatorius, 484 Abuta spp., 371 Acacia spp., 771 Acetylcholine, 262, 518 Acetylomithine, 170, 171, 172 Achillea spp., 779 Achilleine achilletine, 779 Acolyctine, 686 Aconine, 673, 675, 679, 685 Aconines, nuclear structure, 693 Aconite alkaloids, 673 Aconitine, 673, 674, 775 oxidation products, 676 Aconitines, pharmacological action, 690 Aconitinone, 676 Aconitoline, 675... 

Aconite alkaloids Aconitine, molecular formula C34H47NO11, is an example of an aconite alkaloid. It is soluble in organic solvents, e.g. CHCI3 and CeHg, and sfightly soluble in alcohol or ether, but insoluble in water. Aconitine is an extremely toxic substance obtained from the plants of the genus Aconitum (family Ranunculaceae), commonly known as aconite or monkshood . It is a neurotoxin, and used for creating models of cardiac arrhythmia. 

Research on diterpenoid alkaloids published during the past year has continued to expand the body of structural and synthetic information available on these complex plant bases. The structures of ten new alkaloids from Aconitum and Delphinium species, including seven new bisditerpenoid alkaloids, have been reported. Tlie most significant progress in methods of structure elucidation has been the very successful applications of n.m.r. to the study of complex diterpenoid alkaloids. The New Bruns wick group under Professor Karel Wiesner has continued its progress toward the syntheses of the Ci9-aconitine-type alkaloids. An historical account of the synthesis of talatisamine (1), the first synthesis of a hexacyclic aconite alkaloid, has been published. This work was reviewed in a previous Report. ... 

Figure 1. Structures of aconite alkaloids investigated. Copyright 1986 American Cyanamid Co. Reprinted with permission.

Many alkaloids have methyl groups on nitrogen or on oxygen or the equivalent methylene groups on two oxygens. It is notable that other alkyl groups are never present except in the rather special cases of the Aconite alkaloids, and therefore methylation is in a special position which as recent investigations have shown follows well-defined principles (186, 388-391). 

An interesting review of the development of the synthesis of the Aconite alkaloids has appeared. ... 

Synthetic studies of hetisan-t5rpe aconite alkaloids (total synthesis of ( )-nominine) 06Y237. 

K. Wiesner, Systematic Development of Strategy in the Synthesis of Polycyclic Polysubstituted Natural Products The Aconite Alkaloids , Chem. Soc. Rev. 1977, 6,413. 

E. Fujita and coworkers carried out chemical conversions of trichokaurin (56) to a keto acid (127) and of enmein (62) to triol (126). Compounds (126) and (127) had been converted into r-16-kaurene (116) and three aconite alkaloids (atisine, garryine, and veatchine) by Masamune and coworkers hence these chemical conversions imply a formal chemical conversion of trichokaurin and enmein to /-16-kaurene and three aconite alkaloids. 

Tulyaganov NT, Dzhakhangirov FN, Sadritdinov FS, Khamdamov I (1976) Pharmacology of aconite alkaloids. In Sultanov MB (ed) Farmakologiia Rastitelnuikh Veshestv (Pharmacology of plant substances). FAN, Tashkent, pp 76-91 (in Russian)... 

Research studies on the aconite alkaloids started at the beginning of the nineteenth century, and aconitine was isolated from Actinidia napellus in 1833. As for the Aconitum plants of Japan, Shimoyama made the first report in 1882, and the plain chemical structure of aconitine was reported in the 1950s [4]. The stereochemistry, including absolute configuration, of the aconitine skeleton was determined when the total synthesis delphinine, an aconitine-related alkaloid, was achieved in 1972 [5-7]. 

K. Wiesner, Some Highlights in the Structural and Synthetic Chemistry of the Aconite Alkaloids. A Personal Historical Perspective, Tetrahedron, 1985, 4 , 485. 

Song J-Z, Han Q-B, Qiao C-F, But PP-H, Xu H-X (2010) Development and validation of a rapid capillary zone electrophoresis method for the determination of aconite alkaloids in Aconite roots. Phytochem Anal 21 137-143. doi 10.1002/pca.ll68... 

Muratake H, Natsume M. Total synthesis of ( )-nominine, a heptacyclic hetisine-type aconite alkaloid. Angew. Chem. Int. Ed. 2004 43 4646 649. 

In the total synthesis of the hesitine-type aconite alkaloid nominine, the C-ring was constructed by radical cyclization to form 118 from the enyne precursor 117. ° In the first step, the tin radical reacted with alkyne 117 to form a radical that underwent a 6-exo-trig radical cyclization. The resulting radical was trapped by BuaSnH to give a vinyl stannane, which afforded 117 after destannylation with SiOi (Scheme 25.56). 

The kaurane and atisane diterpenes, in a variety of forms, serve as substrates for the elaboration of an array of complex, highly functionalized natural products including the gibberellins, the grayanotoxins, and the aconite alkaloids e.g., talatizidine, 286). The biogenesis of each of these... 

The overall transformation of the atisane skeleton e.g. atiserene, 274) to the Ci9 aconite alkaloids, apart from oxidative and functionalization steps, requires three principal structural alterations C7-C20 bond connection, removal of one carbon (C17), and rearrangement of the Cg-Cg bond to C15. Although the order of these alterations is not known, the isolation of the atisine-type alkaloid, denudatin (285), which possesses the C7-C20 link, indicates that this step may occur first. 

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