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Configuration‐Dependent Ring Opening of Silyloxiranes: Synthesis of Functionalized Alkenes or Tetrahydrofurans
Author(s) -
Lange Jens,
Schaumann Ernst
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900448
Subject(s) - chemistry , hydrosilylation , silylation , ring (chemistry) , silanes , nucleophile , medicinal chemistry , bromide , epoxide , sulfide , leaving group , stereochemistry , organic chemistry , silane , catalysis
cis ‐ and trans ‐Silyloxiranes with a potential tosylate or bromide leaving group in the β position are available by the diastereospecific reduction of the corresponding alkynes with DIBAL‐H and hydrosilylation with silanes, respectively. In the reaction with the anion of a silylthioacetal, the outcome of the reaction is configuration dependent: the cis ‐oxiranes add nucleophilic methanthiolate and give a cis ‐vinyl sulfide unit in a Peterson olefination. In contrast, the trans ‐oxiranes lead to functionalized tetrahydrofurans with silyl(methylthio) substitution on the ring and in the exocyclic α position. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)