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

被引:106
|
作者
Peryshkov, Dmitry V. [1 ]
Schrock, Richard R. [1 ]
Takase, Michael K. [1 ]
Mueller, Peter [1 ]
Hoveyda, Arnir H. [2 ]
机构
[1] MIT, Dept Chem 6 331, Cambridge, MA 02139 USA
[2] Boston Coll, Dept Chem, Merkert Chem Ctr, Chestnut Hill, MA 02467 USA
基金
美国国家科学基金会; 美国国家卫生研究院;
关键词
METAL-CARBON BONDS; METALLACYCLOBUTANE COMPLEXES; TANTALUM COMPLEXES; CATALYSTS; MOLYBDENUM; REACTIVITY; MO; B(C6F5)(3); PRECURSORS; NIOBIUM;
D O I
10.1021/ja210349m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Addition of LiOHMT (OHMT = O-2,6-dimesitylphenoxide) to W(O)(CH-t-Bu)(PMe2Ph)(2)Cl-2 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)(Me(2)Pyr)(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 (similar to 20% Z).
引用
收藏
页码:20754 / 20757
页数:4
相关论文
共 50 条
  • [1] Cyclometalated Ruthenium Alkylidene Complexes: A Powerful Family of Z-Selective Olefin Metathesis Catalysts
    Marx, Vanessa M.
    Rosebrugh, Lauren E.
    Herbert, Myles B.
    Grubbs, Robert H.
    [J]. RUTHENIUM IN CATALYSIS, 2014, 48 : 1 - 17
  • [2] Molybdenum chloride catalysts for Z-selective olefin metathesis reactions
    Koh, Ming Joo
    Nguyen, Thach T.
    Lam, Jonathan K.
    Torker, Sebastian
    Hyvl, Jakub
    Schrock, Richard R.
    Hoveyda, Amir H.
    [J]. NATURE, 2017, 542 (7639) : 80 - +
  • [3] Molybdenum chloride catalysts for Z-selective olefin metathesis reactions
    Ming Joo Koh
    Thach T. Nguyen
    Jonathan K. Lam
    Sebastian Torker
    Jakub Hyvl
    Richard R. Schrock
    Amir H. Hoveyda
    [J]. Nature, 2017, 542 : 80 - 85
  • [4] Recent Developments in Z-Selective Olefin Metathesis Reactions by Molybdenum, Tungsten, Ruthenium, and Vanadium Catalysts
    Dawood, Kamal M.
    Nomura, Kotohiro
    [J]. ADVANCED SYNTHESIS & CATALYSIS, 2021, 363 (08) : 1970 - 1997
  • [5] Z-selective olefin metathesis with ruthenium catalysts
    Keitz, Benjamin K.
    Endo, Koji
    Herbert, Myles B.
    Patel, Paresma R.
    Grubbs, Robert H.
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2012, 243
  • [6] Molybdenum imido alkylidene and tungsten oxo alkylidene N-heterocyclic carbene complexes for olefin metathesis
    Suman Sen
    Roman Schowner
    Michael R. Buchmeiser
    [J]. Monatshefte für Chemie - Chemical Monthly, 2015, 146 : 1037 - 1042
  • [7] Molybdenum imido alkylidene and tungsten oxo alkylidene N-heterocyclic carbene complexes for olefin metathesis
    Sen, Suman
    Schowner, Roman
    Buchmeiser, Michael R.
    [J]. MONATSHEFTE FUR CHEMIE, 2015, 146 (07): : 1037 - 1042
  • [8] OLEFIN METATHESIS BY MO AND W OXO ALKYLIDENE COMPLEXES
    SCHROCK, RR
    WENGROVIUS, J
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1980, 180 (AUG): : 201 - INOR
  • [9] Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis
    Keitz, Benjamin K.
    Endo, Koji
    Patel, Paresma R.
    Herbert, Myles B.
    Grubbs, Robert H.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (01) : 693 - 699
  • [10] Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis
    Endo, Koji
    Grubbs, Robert H.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (22) : 8525 - 8527