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Syntheses of (+)‐( S , S )‐( cis ‐6‐Methyltetrahydropyran‐2‐yl)acetic acid and of (−)‐( R , R )‐Didesoxy‐pyrenophorine Using a New d 5 ‐Reagent . Preliminary communication
Author(s) -
Seebach Dieter,
Phmakotr Manat
Publication year - 1979
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.19790620322
Subject(s) - chemistry , synthon , reagent , nucleophile , epoxide , derivative (finance) , beckmann rearrangement , acetic acid , ring (chemistry) , stereochemistry , hydrolysis , lactone , combinatorial chemistry , organic chemistry , oxime , financial economics , economics , catalysis
The Li/K‐derivative 6 is used to synthesize the title compounds ( 3a and 4a ) in enantiomerically pure form from (−)‐( S )‐propylene epoxide. The C,C bond forming key step leading to the hydroxyketone 7 is followed by cyclization (→, 8 ), Beckmann cleavage (→ 9b ) and hydrolysis to 3a (recently isolated from civet). Base treatment of 3a opens the ring ( 10 ) to give the hydroxyacid 1 which is cyclized to the macrolide 4a . The synthetic usefulness of the highly nucleophilic doubly reduced dienone system 6 as d 5 ‐reagent (see synthons 2) is thus demonstirated.