Azepine alkaloid

Plunkett AO (1994) Pyrrole, pyrrolidine, pyridine, piperidine, and azepine alkaloids. Nat Prod Rep 11 581-590... 

Klingsberg, E. and Newkome, G.R., Eds., Pyridine and Its Derivatives, Interscience, New York, 1960 Schoefield, K., Heteroaromatic Nitrogen Compounds Pyrroles and Pyridines, Butterworths, London, 1967 Hurst, D.T., An Introduction to the Chemistry and Biochemistry and Pyrimidines, Purines, and Ptreridines, J. Wiley, Chichester, UK, 1980 Plunkett, A.O., Pyrrole, pyrrolidine, pyridine, piperidine, and azepine alkaloids, Nat. Prod. Rep. 11, 581-590, 1994 Kaiser, J.P., Feng, Y., and Bollag, J.M., Microbial metabolism of pyridine, quinoline, acridine, and their derivatives under aerobic and anaerobic conditions, Microbiol. Rev. 60, 483-498, 1996. 

Research progress on the synthesis of pyrrolo[l,2-(j]azepine alkaloid stenine 13CJ01186. 

Ye et al. reported the isolation and the stmctural elucidation of cochinchistemo-nine 26, a pyrido[1,2-a]azepine alkaloid from the roots of Stemona cochinchinensis. In that paper, the authors also reported the proposed biogenetic origin. The major alkaloid, stemokerrin 27, proposed as starting material, could be hydrolyzed to form the intermediate 28. Intramolecular aldol condensation of ketone groups at C-9 and... 

Chalciporone 30, a 2-//-azepine alkaloid, is found in the mushroom Chalciporus piperatus (Basidiomycetes). In order to prove the structure and establish the absolute configuration of this unique alkaloid 2//-azepines, their derivatives were synthetized [17-20],... 

N-Subst. pyrrolidines. A 10 M soln. of BH3-dimethyl sulfide in THF added dropwise via syringe to a soln. of startg. succinamic ester in the same solvent under N2, the mixture refluxed 7-9 h, and quenched with methanol and 2 N NaOH N-phenylpyr-rolidine. Y 82%. The method failed for highly hindered amines. F.e. incl. N-subst. piperidines s. M.C. Venuti, O. Ort, Synthesis 1988, 985-8 review of pyrrole, pyrrolidine, piperidine, pyridine and azepine alkaloids (1986-7 literature) s. A.R. Pinder, Nat. Prod. Reports 6, 67-78 (1989). 

T r y p t"o p h a n, 3-hydroxyanthranilic acid, quinoline, acridine and benzodi azepine alkaloids... 

Sturm S, Schinnerl J, Greger H, Stuppner H (2008) Nonaqueous capillary electrophoresis-electrospray ionization-ion trap-mass spectrometry analysis of pyrrolo- and pyrido[l,2-a] azepine alkaloids mStemona. Electrophoresis 29 2079-2087. doi 10.1002/elps.200700860... 

Dibenz[h,e]azepine-6,11-diones ent-Morphinan nomenclature, 1, 29 Morphinan, 1,2,3,4-tetrahydro-nomenclature, 1, 29 14-a-Morphinan, N-methyl-synthesis, 1, 480 Morphinans nomenclature, 1, 29 as pharmaceuticals, 1, 148 synthesis, 2, 377 Morphine, 2, 512 as analgesic, 1, 167 as metabolite of normorphine, 1, 235 as pharmaceutical, 1, 146, 147, 148 synthesis, 1, 480 Morphine alkaloids structure, 4, 534 Morphin-7-en nomenclature, 1, 29 Morphinone, dihydro-as pharmaceutical, 1, 147 Morpholine — see also 1,4-Oxazine, tetrahydrocarcinogenicity, 1, 229 corrosion inhibitor, 1, 409 metabolism, 1, 226 nomenclature, 3, 996 structure, 2, 5 synthesis, 2, 89 Morpholine, 4-aciyloyl-polymers, 1, 291 Morpholine, alkenyl-polymers, 1, 291... 

Additionally, uracil 6-iminophosphorane, isocyanate, and o-methyl-e-caprolactim ether join to form the intensely yellow pyrimido[4 5 4,5] pyrimido[6,l-n]azepine (360), as shown in Scheme 130. Upon ring closure, methanol is spontaneously eliminated. Diethyl azodicarboxylate affords with the other components pyrimido[4,5-e][l,2,4]triazoline (361), which is closely related to the alkaloid isofervenuline. The imidazo[5, -/][ ,2,4]tria-zine (362) results in a known Michael-type rearrangement sequence by treatment with diethyl acetylenedicarboxylate (86JOC149, 86JOC2787) in this latter case, the Michael-type addition occurs much faster than the expected three-component reaction [93H(35)1055]. 

Spongiacidins A (197) and B (198), azepine-type bromopyrrole alkaloids from Hymeniacidon which are geometrical isomers of hymenialdisine (171), inhibit c-erbB-2 kinase (IC50 9.0 and 8.5 pg/ml) and cyclin dependent kinase 4 (IC50 32 and 12 pg/ml) [157],... 

Studies directed toward the synthesis of amaryllidaceae alkaloids provide instructive examples of the combined use of spirocylization and Michael addition pathways in phenolic oxidations (03MI1). For example, treatment of the norbelladine derivative 164 with BTIB leads, by way of C,C-bond formation, to the spiroannulated azepine 165 (Scheme 47) (96JOC5857, 98JOC6625). Hydrolysis of the amide moiety in 165 results in Michael addition of the nitrogen center to the dienone ring and affords ( )-oxomaritidine (166). BTIB-oxidation of the appropriate... 

Ring construction approaches have also been used effectively in the diastereoselective synthesis of the fused azepine 43 from the pyrrolidinone 41 and (Z)-l,4-dichloro-2-butene 42 [01TA2205], and in the synthesis of the alkaloid 275A (44) from the Colombian poison frog Dendrobates lehmanni [01JNP421]. 

For the synthesis of pandoline (284) and 20-epi-pandoline (285), the epoxy-aldehyde (286) was condensed with the indolo-azepine (278) (Scheme 40) the result was an equimolecular mixture of the two alkaloids, in total yield of 64%, based on (278). In accordance with earlier observations, pandoline and 20-epi-pandoline can be reduced to the velbanamine derivatives (287) and (288), which can be isomerized to the C-16 epimers (289) and (290). These compounds contain, respectively, the complete structure and stereochemistry of the non-vindoline component of the oncolytic alkaloids leurosidine and vinblastine. 

Finally, condensation of the indolo-azepine (278) with 4-chlorobutanal gave107 an epimeric mixture of intermediate quaternary salts, formulated as (291), either of which, on reaction with triethylamine, suffered fragmentation and re-cyclization, with formation of desethylibophyllidine (292), which is the alkaloid recently isolated14e from Tabernaemontana albiflora (Scheme 41). 

The heterocyclic hemi-aminal 44 was formed as a model for the synthesis of the marine alkaloids zoanthamine and zoanthenol and is derived from the cyclic imine formed by the reduction of an appropriated substituted azide <07H(72)213>. A pyrrolidine-fused azepine has been isolated from the venom of the ant Myrmicaria melanogaster and assigned as 45 based upon GC and FT-IR comparison with synthetic material <07JNP160>. The axially chiral doubly bridged biphenyl azepine 46 has been synthesised and used with oxone as an epoxidation catalyst in a biphasic system <070BC501>. 

The synthesis of C-4/C-10 cyclic bromopyrrole alkaloids has been intensively explored, and several approaches to their pyrrolo[2,3-c]azepin-8-one ring system (bearing an imidazole-derived ring at position 4) have been proposed [63-65]. 

A new Stemona alkaloid sessilifoliamide C, 41 (from Stemona sessilifolia) has been described with a fused azepine skeleton a butanolide analogue (sessilifoliamide B) was also isolated <03T7779>. 

Once again, ammonium ylides display higher diastereoselectivities than their sulfur counterparts. This observation formed the basis of a recent synthetic approach towards the alkaloid makomakine (331 Scheme 87) where the key step was the ring contraction of the azepine (329) into the cw-substituted piperidine ring (330). ° ... 

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