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Synthesis of ( R )‐1,2,11‐trihydroxy‐, ( R )‐2,11‐, and ( R )‐2,10‐dihydroxyaporphines — non naturally occurring aporphine alkaloids from pukateine and thebaine
Author(s) -
Ram Vishnu J.,
Neumeyer John L.
Publication year - 1991
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570280713
Subject(s) - chemistry , thebaine , methanesulfonic acid , hydrobromic acid , dichloromethane , hydrogenolysis , acetic acid , ammonia , medicinal chemistry , noscapine , organic chemistry , stereochemistry , alkaloid , catalysis , medicine , codeine , morphine , solvent , pharmacology
The synthesis of ( R )‐2,10‐dihydroxyaporphine ( 3a ), ( R )‐2,10‐dihydroxy‐ N‐n ‐propylnoraporphine ( 3b ) from thebaine and ( R )‐2,11‐dihydroxyaporphine (7), and 1,2,11‐trihydroxyaporphine ( 9 ), from pukateine is reported. The rearrangement of thebaine and northebaine with methanesulfonic acid to 1a and 1b with subsequent N ‐propylation gave 1b . Tetrazolyation of 1a, 1b and hydrogenolysis of 2a and 2b on Pd/C in acetic acid with subsequent O‐demethylation with hydrobromic acid (48%) led to 3a and 3b . R (‐)‐2,11‐Dihydroxyaporphine ( 7 ) was prepared by lithium/ammonia reduction of pukateine. ( R )‐1,2,11‐Trihydroxyaporphine ( 9 ) was synthesized by reaction of pukateine with boron tribromide in dichloromethane.