Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes
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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).
创建时间:
2016-02-22



