Premium
New Olefinic Cyclizations by Oxymetallation. Conversion of (−)‐elemol to (−)‐selina‐4α, 11‐diol (cryptomeridiol) and (−)‐guai‐1 (10)‐ene‐4α, 11‐diol
Author(s) -
Renold Walter,
Ohloff Günther,
Norin Torbjörn
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.19790620409
Subject(s) - chemistry , diol , lithium aluminium hydride , ene reaction , organic chemistry , camphor , stereochemistry
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.