Coupling of propargylsilanes with Fischer carbene chromium complexes: a new synthesis of conjugated dienes

The reaction of secondary propargylsilanes with Fischer carbene complexes affords conjugated dienes through a process involving alkyne insertion, followed by a 1,2-silicon shift, followed by decomplexation. If a primary propargylsilane is employed, the silicon does not shift and normal alkyne-Fische...

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Bibliographic Details
Published inJournal of organometallic chemistry Vol. 689; no. 21; pp. 3379 - 3387
Main Authors Patel, Paren P., Zhu, Yixin, Zhang, Lei, Herndon, James W.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 15.10.2004
Subjects
Alkynes
Carbene complexes
Chromium
Dienes
Silicon migration
Chromium
Carbene complexes
Dienes
Silicon migration
Alkynes
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Summary:The reaction of secondary propargylsilanes with Fischer carbene complexes affords conjugated dienes through a process involving alkyne insertion, followed by a 1,2-silicon shift, followed by decomplexation. If a primary propargylsilane is employed, the silicon does not shift and normal alkyne-Fischer carbene coupling processes are observed. The reaction of propargylsilanes with Fischer carbene complexes has been examined. If the silane-containing carbon is secondary the predominant pathway involves formation of conjugated dienes through a 1,2-silicon shift process of the initially formed vinylcarbene complex intermediate. If a primary propargylsilane is employed, the silicon does not shift and normal alkyne-Fischer carbene coupling processes are observed. The process is moderately stereoselective, resulting in the E enol ether and Z alkenylsilane.
ISSN:0022-328X
1872-8561
DOI:10.1016/j.jorganchem.2004.07.051