Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes

Addition of LiOHMT (OHMT = O-2,6-dimesitylphenoxide) to W(O)(CH-t-Bu)(PMe2Ph)2Cl2 led to WO(CH-t-Bu)Cl(OHMT)(PMe2Ph) (4). Subsequent addition of Li(2,5-Me2C4H2N) to 4 yielded yellow W(O)(CH-t-Bu)(OHMT)(Me2Pyr)(PMe2Ph) (5). Compound 5 is a highly effective catalyst for the Z-selective co...

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Veröffentlicht in:	Journal of the American Chemical Society 2011-12, Vol.133 (51), p.20754-20757
Hauptverfasser:	Peryshkov, Dmitry V, Schrock, Richard R, Takase, Michael K, Müller, Peter, Hoveyda, Amir H
Format:	Artikel
Sprache:	eng
Schlagworte:	Alkenes - chemistry Catalysis Coordination Complexes - chemistry Molecular Conformation Tungsten - chemistry
Online-Zugang:	Volltext
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Zusammenfassung:	Addition of LiOHMT (OHMT = O-2,6-dimesitylphenoxide) to W(O)(CH-t-Bu)(PMe2Ph)2Cl2 led to WO(CH-t-Bu)Cl(OHMT)(PMe2Ph) (4). Subsequent addition of Li(2,5-Me2C4H2N) to 4 yielded yellow W(O)(CH-t-Bu)(OHMT)(Me2Pyr)(PMe2Ph) (5). Compound 5 is a highly effective catalyst for the Z-selective coupling of selected terminal olefins (at 0.2% loading) to give product in >75% yield with >99% Z configuration. Addition of 2 equiv of B(C6F5)3 to 5 afforded a catalyst activated at the oxo ligand by B(C6F5)3. 5·B(C6F5)3 is a highly active catalyst that produces thermodynamic products (∼20% Z).
ISSN:	0002-7863 1520-5126
DOI:	10.1021/ja210349m