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Synthesis of Aristotelia ‐type alkaloids. Part V . Biomimetic synthesis of (±)‐aristomakine and (±)‐aristomakinine
Author(s) -
Burkard Stefan,
Borsehberg HansJürg
Publication year - 1990
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19900730209
Subject(s) - chemistry , iminium , isopropyl , biomimetic synthesis , stereochemistry , alkaloid , fragmentation (computing) , indole test , hydrolysis , ion , organic chemistry , computer science , operating system
Biomimetic syntheses of racemic aristomakinine ((±)‐ 3 ) and aristomakine ((±)‐ 4 ), an unusual indole alkaloid bearing an N ‐isopropyl group, are described. The key step is a Grob ‐type fragmentation of anti ‐15‐aristotelinyl methanesulfonate ((±)‐ 2 ) to the intermediate iminium ion I which, upon subsequent hydrolysis, furnished aristomakinine ((±)‐ 3 ). On the other hand, the same intermediate could be reduced in situ to aristomakine ((±)‐ 4 ). The controversial relative configurations of the two alkaloids have been firmly established by means of NOE difference experiments.