Studies on the syntheses of heterocyclic compounds. Part CCC. Syntheses of salutaridine, sinoacutine, and thebaine. Formal total syntheses of morphine and sinomenine

Abstract

The diazotisation of (*)-I -(2-amino-3-benzyloxy-4-methoxybenzyl) -1,2,3,4-tetrahydro-6,7-dimethoxy-2methylisoquinoline (VIII) followed by the thermal decomposition of the resulting diazoniurn salt, gave ( f ) -salutaridine (11) [or (f)-sinoacutine], which was converted into (*)-thebaine (111). The 2-aminobenzylisoquinoline (VIII) was resolved, and the (-)and (+) -enantiomers (VIIIa and b) were used for the syntheses of salutaridine (IIa), sinoacutine (IIb), and thebaine (IIIa) and its antipode (IIIb). This work also constitutes the fifth total synthesis of morphine (I).

New alkaloids sinomacutines A–E, and cephalonine-2-O-β-d-glucopyranoside from rhizomes of Sinomenium acutum

“…Positive Cotton effect at 300 nm and negative Cotton effect at 340 nm confirmed that the absolute configuration of subunit 'c' was same as that of 8. 16 Consequently, the structure of 2 was fully established, and named as sallisonine B.…”

Alkaloids

“…Representative morphine alkaloids are morphine (200), codeine (201), thebaine (202), salutaridine (203), pallidine (204), flavinantine (205), and sinomenine (206). The structures of these alkaloids were elucidated by a combination of Hofmann degradation and IR, UV, NMR, and mass spectroscopies.…”

“…Total synthesis of morphine (200) was achieved first by Gates [197] and then by Ginsburg [198]. It has also been prepared by Barton and his associates [199] with biogenetictype sequences.…”

“…It has also been prepared by Barton and his associates [199] with biogenetictype sequences. Kametani and his associates reported the synthesis of the key intermediate salutaridine (203) by the Pschorr reaction of the aminoisoquinoline 207 [200] as well as by photolysis of 2 -bromoreticuline (208, racemic mixture) [201].…”

“…Morphine (200) Preparation. One method for the production of morphine and codeine starts from finely powdered poppy plants [202].…”