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Synthese von (+)-(5S, 6S)-Azafrin-methylester; absolute Konfiguration von Aeginetinsäure and von weiteren vicinalen Apocarotin-diolen

✍ Scribed by Walter Eschenmoser; Peter Uebelhart; Conrad Hans Eugster


Publisher
John Wiley and Sons
Year
1982
Tongue
German
Weight
731 KB
Volume
65
Category
Article
ISSN
0018-019X

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✦ Synopsis


Synthesis of (+)‐(5__S__, 6__S__)‐Azafrin Methyl Ester; Absolute Configuration of Aeginetic Acid and of Further Vicinal Apocarotenediols

We describe the synthesis of a series of optically active vicinal apo‐β‐carotenediols. Thus, starting from (+)‐(5__S__, 6__S__)‐5,6‐dihydroxy‐5,6‐dihydro‐β‐ionone (2) we have prepared the (Z/E)‐isomeric (+)‐C~15~‐esters 7 and 8, the (+)‐retinoic derivatives 14, 15, 18, 19 and (+)‐methyl azafrinate (22), the enantiomer of the naturally occur‐ring compound (s. Scheme 1). Our synthesis also establishes the absolute configura‐tion of aeginetic acid (24), aeginetoside (25) and aeginetin (26), compounds isolated from the root parasite Aeginetia indica by Indian and Japanese workers (s. Scheme 2).

The presented synthesis of optically active methyl azafrinate confirms our previous assignment [14] of the absolute configuration of azafrin (1a), which was based on degradative evidence.