Morphinandienone alkaloids, synthesis

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. ... 

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. 

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... 

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... 

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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