What is the initiation step of the Grubbs-Hoveyda olefin metathesis catalyst?

被引：82

作者：

Ashworth, Ian W. ^{[2
]}

Hillier, Ian H. ^{[1
]}

Nelson, David J. ^{[3
]}

Percy, Jonathan M. ^{[3
]}

Vincent, Mark A. ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

[2] AstraZeneca Global Res & Dev, Macclesfield SK10 2NA, Cheshire, England

[3] WestCHEM Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland

来源：

CHEMICAL COMMUNICATIONS | 2011年 / 47卷 / 19期

基金：

英国工程与自然科学研究理事会;

关键词：

MECHANISM; DENSITY;

D O I：

10.1039/c1cc11230a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Density function theory calculations reveal that the Grubbs-Hoveyda olefin metathesis pre-catalyst is activated by the formation of a complex in which the incoming alkene substrate and outgoing alkoxy ligand are both clearly associated with the ruthenium centre. The computed energies for reaction are in good agreement with the experimental values, reported here.

引用

页码：5428 / 5430

页数：3

共 14 条

[1] Relevance of cis- and trans-dichloride Ru intermediates in Grubbs-II olefin metathesis catalysis (H2IMesCl2Ru=CHR) [J].

Benitez, Diego ;

Tkatchouk, Ekaterina ;

Goddard, William A., III .

CHEMICAL COMMUNICATIONS, 2008, (46) :6194-6196

[2]

Frisch M., 2004, GAUSSIAN 03 REVISION, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014

[3] Efficient and recyclable monomeric and dendritic Ru-based metathesis catalysts [J].

Garber, SB ;

Kingsbury, JS ;

Gray, BL ;

Hoveyda, AH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (34) :8168-8179

[4] Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations [J].

Hillier, Ian H. ;

Pandian, Shanthi ;

Percy, Jonathan M. ;

Vincent, Mark A. .

DALTON TRANSACTIONS, 2011, 40 (05) :1061-1072

[5] A recyclable Ru-based metathesis catalyst [J].

Kingsbury, JS ;

Harrity, JPA ;

Bonitatebus, PJ ;

Hoveyda, AH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (04) :791-799

[6]

Lloyd-Jones G. C., 2006, INVESTIGATION ORGANI, P343

[7] Prediction of ring formation efficiency via diene ring closing metathesis (RCM) reactions using the M06 density functional [J].

Pandian, Shanthi ;

Hillier, Ian H. ;

Vincent, Mark A. ;

Burton, Neil A. ;

Ashworth, Ian W. ;

Nelson, David J. ;

Percy, Jonathan M. ;

Rinaudo, Giuseppe .

CHEMICAL PHYSICS LETTERS, 2009, 476 (1-3) :37-40

[8] Mechanism and activity of ruthenium olefin metathesis catalysts [J].

Sanford, MS ;

Love, JA ;

Grubbs, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (27) :6543-6554

[9] New insights into the mechanism of ruthenium-catalyzed olefin metathesis reactions [J].

Sanford, MS ;

Ulman, M ;

Grubbs, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (04) :749-750

[10] DFT Mechanistic Study on Diene Metathesis Catalyzed by Ru-Based Grubbs-Hoveyda-Type Carbenes: The Key Role of Tr-Electron Density De localization in the Hoveyda Ligand [J].

Solans-Monfort, Xavier ;

Pleixats, Roser ;

Sodupe, Mariona .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (24) :7331-7343

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