Macrocyclic spermidine alkaloids

Two macrocyclic spermidine alkaloids have been isolated from whole plants of Clerodendrum myricoides (Verbenaceae). Myricoidine (104) is accompanied by its reduced derivative dihydromyricoidine (105). These two bases are present in C. myricoides in minute amounts (ca. 10 ppm from the dried plant) and were isolated as homogeneous compounds by repeated countercurrent distribution (97). 

The macrocyclic spermidine alkaloid pleurostyline," isolated from the leaves of Pleurostylia africana, has structure (26). Aphelandrine, obtained from the roots of Aphelandra squarrosa, has been assigned structure (27 R = H). It is present in eight other species of Aphelandra and also in Encephalosphaera lasiandra its O-methyl ether (27 R = Me) was isolated only from Aphelandra sinclairianOy however. 

Scheiper, B. Glorius, E Leitner, A. Fiirstner, A. Catalysis-based enantioselective total synthesis of the macrocyclic spermidine alkaloid isooncinotin. Proc. Natl. Acad. Sci. 2004, 101, 11960-11965. 

A high-yield synthesis of the macrocyclic spermidine alkaloids (97) involves the boron-template cyclization of the aminoborane intermediate (98), and... 

Macroheterocyclization.1 s Pd(0) can catalyze macrocyclizations which form a C—N bond. This reaction was used in a synthesis of the spermidine alkaloid inandenine-12-one (1). 

The inandenines are macrocyclic spermidine derivatives that have been isolated as ketones from Oncinot is species. The main alkaloids of the leaves of O. inandensis inandenin-12-one (53) and inandenin-13-one (54), exist as a mixture that has not yet been separated. Only by chemical degradation of the mixture to the ethylene acetal derivatives 55 and 56 it has been estab-... 

Hesse, M. and Schmidt, H. (1977) Macrocyclic spermidine and spermine alkaloids. In Wiesner K (Ed.) MTP International Revies of Science, Series 2, Vol. 9, Butterworths, London, 265-307. 

Trost and Cossy [165] developed this method to construct the macrocyclic ring of the spermidine alkaloid inandenin-12-one (274). As shown in Scheme 92, subjection of amino ketone 272 to 10 mol% of (Ph3P)4Pd and 8 mol% of... 

Macrocyclic spermin and spermidin alkaloids, total synthesis of ... 

Fig. 10. Macrocyclic spermidine and spermine alkaloids from higher plants.

Badwani, M. M., K. Bernauer, P. van den Broek, D. Grocer, A. Guogisberg, S. Johne, I. Kompis, F. Schneider, H. Vetth, M. Hesse, and H. Schmid, Macrocyclic spermidine and spermine alkaloids. Pure Appl. Chem., 33, 81-108 (1973). 

Macrocyclic Lactams.— Two spermidine alkaloids have been prepared by the reaction of spermidine itself with a thiazolidine 2-thione diamide derivative under high-dilution conditions the two regioisomers produced were separated by chromatography.An interesting boron-template cyclization of the amino-ester (173) to the lactam (174) has been used to prepare several members of the celacinnine group of natural products (Scheme 85). ... 

Macrocyclic polyazaheterocycles include the well known spermidine alkaloids, the synthesis of which has attracted a great deal of attention over the past few years. An efficient 6-step total synthesis " of the dihydroperiphylline system (218), which has recently been isolated from plant sources, has been reported. 

M. loesner Urb. and M. buxifolia (A. Rich) Griseb collected on the island of Cuba have been extensively studied by H. Ripperger et al. [46-47] who isolated a series of new macrocyclic alkaloids of the spermidin type, commonly found in the Celastraceae family the new alkaloids could be related to others already obtained by Kupchan s group. 

There is no uniform classification for the A. In the literature divisions according to origin (examples Aconitum, Amaryllidaceae, Aspidosperma, cactus, Catharanthus, Cephalotaxus, Cinchona, coca, Corydalis, curare, Dendrobates, ergot, Erythrina, Iboga, Lycopodium, Maytenus, opium, Rauvol-fia, Senecio, Strychnos, tobacco, Vinca alkaloids, salamander, Solanum, Veratrum steroid alkaloids) in addition to divisions according to chemical structure (examples aporphine, benzylisoquinoline, bis-benzylisoquinoline, berberine, carboline, diterpene, inudazole, indole, indolizidine, isoquinoline, lupinane, macrocyclic, morphine, peptide, / -phenyl-ethylamine, piperidine, purine, pyridine, pyrrolidine, pyrrolizidine, quinoline, quinolizidine, quinucli-dine, spermine, spermidine, steroid, terpene, tro-pane, tropolone alkaloids) are used. 

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