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Radikalische Cyclisierung von Dienen, VI. Totalsynthese von (−)‐Coriolin und (−)‐Epicoriolin aus ( S )‐(+)‐Carvon
Author(s) -
Weinges Klaus,
Braum Ralf,
HuberPatz Ursula,
Irngartinger Hermann
Publication year - 1993
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.1993199301181
Subject(s) - chemistry , epimer , stereochemistry , double bond , organic chemistry
Radical‐Type Cyclization of Dines, VI. – Total Synthesis of (−)‐Coriolin and (−)‐Epicoriolin from ( S )‐(+)‐Carvone (3a R ,4 S ,6a S )‐(+)‐4‐(4‐Methoxybenzyloxy)‐6a‐methyl‐3,3a,4,6a‐tetrahydro‐2 H ‐cyclopenta[ b ]furan‐2‐one ( 10 ) and (3a R ,3b R ,4 R ,6a S ,7 S ,7a S )‐(−)‐decahydro‐4,7‐dihydroxy‐3a,5,5‐trimethyl‐3‐methylene‐2 H ‐cyclopenta[ a ]pentalen‐2‐one ( 21 ) are the key intermediates in the synthesis of the title compounds 1 and 1a . Enantiomerically pure 10 is produced from ( S )‐(+)‐carvone ( 4 ) in seven straightforward reactions. Compound 21 is produced from 10 by analogy with the method developed for the synthesis of (−)‐hirsutene. Through the introduction of the double bond into 21 via the silylenolether 23 one arrives at precoriolin 25 , which is converted into (−)‐coriolin ( 1 ) and the C‐3 epimer (−)‐epicoriolin ( 1a ) (63:37) with hydrogen peroxide. The structures of 1 and 1a were confirmed via X‐ray crystallography.