Shamma 1 Aporphines

M. Shamma and H. Guinaudeau, Tetrahedron 40, 479S (1984). Biosynthesis of aporphinoid alkaloids. In addition to monomeric alkaloids, discusses proaporphine- and aporphine-benzyliso-quinoline dimers, dimeric oxidized aporphines, and types derived by catabolism of benzyliso-quinoline-derived dimers. 

Two aporphine-pavine dimers, pennsylpavoline (171, R=H) and pennsylpavine (171, R=Me), together with their aporphine-benz-ylisoquinoline dimer precursors, pennsylvamine and pennsylvan-amine, have been isolated from Thalictrum polyganum (Shamma and Moniot, J.Amer.chem.Soc., 1974, 96, 3338). 

Apart from the reports on aporphine alkaloids published elsewhere in this series of The Alkaloids, there have appeared two reviews (393, 422) and the book by Shamma (1). The isolation of the aporphine alkaloids was also carried out by using ion exchangers (302). 

According to Shamma, Guinaudeau, and collaborators, the quaternary oxo-aporphine thailandine (96) is probably an intermediate in the oxidation of stephanine (94) to oxostephanine (97) (Guinaudeau et al. 1981) (Fig. 21). 

Oxidation of ring B of an aporphine, through the probable intermediacy of a 4,5-dioxoaporphine, is also possible. The product is an aristolochic acid which may in turn be reduced and dehydrated to an aristolactam (Shamma and Guinaudeau 1984) (Fig. 2). 

Shamma M, Lan H-Y, Freyer AJ, Leet JE, Urziia A, Fajardo V (1983) Chiloenamine and Chiloe-nine Two unusual isoquinoline derived alkaloids. A new insight into the catabolism of aporphines. J Chem Soc Commun 799-800... 

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