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New Olefinic Cyclizations by Oxymetallation. Conversion of (−)-elemol to (−)-selina-4α, 11-diol (cryptomeridiol) and (−)-guai-1 (10)-ene-4α, 11-diol

✍ Scribed by Walter Renold; Günther Ohloff; Torbjörn Norin


Book ID
102857414
Publisher
John Wiley and Sons
Year
1979
Tongue
German
Weight
545 KB
Volume
62
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

Acetoxythallation of (−)‐elemol acetate (1b) yields a diacetate 2b which after treatment with lithium aluminium hydride gives (−)‐guai‐1 (10)‐ene‐4α, 11‐diol (2a). (−)‐Elemol (1a) is converted to (−)‐selina‐4α, 11‐diol (9, cryptomeridiol) by hydroxymercuration followed by reductive demercuration. (+)‐γg‐Elemene (5) similarly yields (+)‐selin‐7(11)‐en‐4α‐ol (11, juniper camphor). The stereochemistry and mechanism of these metal salt‐induced olefinic cyclization and their biogenetic implication are discussed.