Morphinandienone alkaloids

The morphinandienone alkaloids themselves can also be electrochemically oxidized. A cyclic voltammogram of morphinandienone (R1, R2 = CH3) 17 in acetonitrile at platinum shows the anodic peaks at 1.15 V and 1.33 V vs. Ag/Ag+. Its preparative anodic oxidation at 1.2 V in CH3CN/0.2 M HBF4 gives trans-10-hydroxy-O-methyl-... 

W. A. Ayer, Alkaloids (London) 6,252-255 (1976) see also earlier volumes. Morphinandienone alkaloids ... 

A reexamination of this plant collected in Sendai gave the two morphinandienone alkaloids sinocutine and pallidine in addition to corynoline, acetylcorynoline, isocorynoline, corynoloxine, protopine, and corycavine (66). 

Synthetic work on morphine and morphinandienone alkaloids continues unabated. Amurine " and O-methylflavinantine have been obtained by the benzyne reaction of appropriate benzyl isoquinoline precursors. A review concerning new synthetic derivatives of dihydrocodeinone is not readily available.Codeine has been prepared in 98% yield from morphine using... 

Morphines and Morphinandienones.—Reviews on the alkaloids of the genus Papaver and the family Papaveraceae have appeared, and a recent detailed review of the morphine alkaloids is now available. Reviews on the synthesis of morphinandienone alkaloids have also been published. ... 

The conversion of reticuline (41) into protoberberine alkaloids (coreximine and scoulerine), a morphinandienone alkaloid (pallidine), and an aporphine alkaloid (isoboldine) by rat-liver enzyme has been reported. ... 

Development and application of new oxidation systems utilizing oxome-talate catalysts, particularly in direct C—H functionalizations of aromatic compounds and in synthesis of morphinandienone alkaloids 12CPB799. 

Morphinandienone Alkaloids (Promorphinanes) Hasubanan Alkaloids Morphine Alkaloids Biosynthesis... 

The in vivo conversion of (/ )-reticuline to morphinandie-nones such as salutaridine (52) (promorphinanes) has been demonstrated (Santavy, 1979) (Fig. 32.18). An enz)mie from a cell-free extract of Papaver somniferum utilized H2O2 to produce salutaridine in high yield. Morphine alkaloids (see below) are derived from the morphinandienone alkaloid salutaridine. 

A record number of new aporphine alkaloids, sixteen, has been isolated and characterized during the year under review. Even better methods for the synthesis of aporphines in high yields have been developed,1-3 and an interesting relationship between aporphines, morphinandienones, neoproaporphines, and spirinedienones has been pointed out.1 A novel and unusual alkaloid is eupolauramine (70), which is structurally related to the aristolactams but which incorporates an additional nitrogen atom in ring A.4... 

In view of this demonstrated facile in vitro conversion of morphinandienones to aporphines, there is now a strong possibility that morphinandienones may as well be in vivo precursors of aporphine alkaloids. ... 

The one and only morphinandienone, (+)-milonine (8,14-Dihydromorphinandienone) (54), was isolated from the dried leaves of Cissampelos sympodialis, a plant used in medicine in northeastern Brazil [50]. Blasko and Cordell reviewed morphinandienone, homomorphinandienone, and other related alkaloids with respect to isolation, structure, elucidation, spectroscopy, and synthesis [94],... 

Bischler-Napieralski and Pictet Spengler reactions continue to serve well for benzylisoquinoline syntheses.76,77 In the latter reaction, use of a-formylphenyl-acetic esters for the non-nitrogen-containing component appears to be advantageous.77 An interesting sequence of reactions (43)—>—>(44) (Scheme 4) has apparently been applied to the synthesis of papaverine [44 R = 3,4-(MeO)2-C6H3CH2 ] and related alkaloids.78 An attempt to convert ( )-reticuline (37 R = H) into a morphinandienone-type alkaloid by enzymic oxidation with... 

Table 3 summarizes reports concerning new sources of alkaloids. All new alkaloids exhibit the increasingly important morphinandienone or the complex and as yet rare hasubanan skeletons. 

Phenethylisoquinoline alkaloids are classified into six major alkaloid groups based on structural differences, namely, simple 1-phenethyliso-quinoline (1), homomorphinandienone (2), bisphenethylisoquinoline (3), homoproaporphine (4), homoaporphine (5), and homoerythrina alkaloids (6). These alkaloids are related to the benzylisoquinoline alkaloids such as morphinandienone, bisbenzylisoquinoline, proaporphine, apor-phine, and erythrina alkaloids. Although colchicine and its derivatives also belong to the phenethylisoquinoline alkaloids group, these alkaloids are not included in this review as they have been reviewed earlier 1). 

Some years ago a general synthetic method 52) for the morphinan-dienone-type alkaloids was discovered by modifying the Pschorr reaction which had been used widely for the synthesis of the aporphine alkaloids and this method was applied to a synthesis of the homo-morphinandienone-type compounds. 

Morphinandienones, recognized as intermediates in the biosynthesis of opium alkaloids (Barton et al. 1965), were obtained in vitro by processes mimicking the plant synthesis (Schwartz and Mami 1975, Szantay et al. 1982, White et al. 1983). When N-formylnorreticuline (39) (Rj = CHO, R2 = H) was brominated at C-6 to (39)... 

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