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A New Variant of the Claisen Rearrangement from Malonate‐Derived Allylic Trimethylsilyl Ketene Acetals: Efficient, Highly Enantio‐ and Diastereoselective Syntheses of (+)‐Methyl Dihydroepijasmonate and (+)‐Methyl Epijasmonate
Author(s) -
Fehr Charles,
Galindo José
Publication year - 2000
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(20000204)39:3<569::aid-anie569>3.0.co;2-8
Subject(s) - ketene , allylic rearrangement , claisen rearrangement , trimethylsilyl , chemistry , kinetic resolution , chirality (physics) , enantioselective synthesis , malonate , carroll rearrangement , stereochemistry , intramolecular force , medicinal chemistry , organic chemistry , catalysis , physics , nambu–jona lasinio model , chiral symmetry breaking , quantum mechanics , quark
Complete chirality transfer occurs in the smooth Claisen rearrangement of the trimethylsilyl (TMS) ketene acetals, which were prepared from allylic malonates ( R )‐ 1 (R=pentyl, 2‐( Z )‐pentenyl). These are in turn accessible by enantioselective reduction/esterification or by enzymatic kinetic resolution. The cis configuration in (+)‐ 3 was achieved by highly syn ‐selective epoxidation of (+)‐ 2 , followed by suprafacial 1,2‐H migration.