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Title: Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis

Abstract

In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.

Authors:
 [1];  [1];  [2];  [1];  [1];  [2];  [2];  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Univ. of California, San Diego, CA (United States)
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1344395
Alternate Identifier(s):
OSTI ID: 1401120
Grant/Contract Number:  
SC0009376; FG02-13ER16370
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 6; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cyclic alkyl amino carbenes; ethenolysis; olefin metathesis; seed-oil derivatives; terminal olefins

Citation Formats

Marx, Vanessa M., Sullivan, Alexandra H., Melaimi, Mohand, Virgil, Scott C., Keitz, Benjamin K., Weinberger, David S., Bertrand, Guy, and Grubbs, Robert H. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis. United States: N. p., 2014. Web. doi:10.1002/anie.201410797.
Marx, Vanessa M., Sullivan, Alexandra H., Melaimi, Mohand, Virgil, Scott C., Keitz, Benjamin K., Weinberger, David S., Bertrand, Guy, & Grubbs, Robert H. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis. United States. doi:https://doi.org/10.1002/anie.201410797
Marx, Vanessa M., Sullivan, Alexandra H., Melaimi, Mohand, Virgil, Scott C., Keitz, Benjamin K., Weinberger, David S., Bertrand, Guy, and Grubbs, Robert H. Wed . "Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis". United States. doi:https://doi.org/10.1002/anie.201410797. https://www.osti.gov/servlets/purl/1344395.
@article{osti_1344395,
title = {Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis},
author = {Marx, Vanessa M. and Sullivan, Alexandra H. and Melaimi, Mohand and Virgil, Scott C. and Keitz, Benjamin K. and Weinberger, David S. and Bertrand, Guy and Grubbs, Robert H.},
abstractNote = {In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.},
doi = {10.1002/anie.201410797},
journal = {Angewandte Chemie (International Edition)},
number = 6,
volume = 54,
place = {United States},
year = {2014},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 39 works
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Figures / Tables:

Figure 1 Figure 1: Selected ruthenium metathesis catalysts previously studied for ethenolysis.

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Works referenced in this record:

A Highly Efficient Olefin Metathesis Process for the Synthesis of Terminal Alkenes from Fatty Acid Esters
journal, June 2012


Useful Products from Complex Starting Materials: Common Chemicals from Biomass Feedstocks
journal, April 2010

  • Marshall, Amanda-Lynn; Alaimo, Peter J.
  • Chemistry - A European Journal, Vol. 16, Issue 17
  • DOI: 10.1002/chem.200903028

Refining of Plant Oils to Chemicals by Olefin Metathesis
journal, May 2012

  • Chikkali, Samir; Mecking, Stefan
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201107645

Fette und Öle als nachwachsende Rohstoffe in der Chemie
journal, March 2011

  • Biermann, Ursula; Bornscheuer, Uwe; Meier, Michael A. R.
  • Angewandte Chemie, Vol. 123, Issue 17
  • DOI: 10.1002/ange.201002767

Metathesereaktionen in der Totalsynthese
journal, July 2005

  • Nicolaou, K. C.; Bulger, Paul G.; Sarlah, David
  • Angewandte Chemie, Vol. 117, Issue 29
  • DOI: 10.1002/ange.200500369

High Oxidation State Multiple Metal−Carbon Bonds
journal, January 2002


Nonproductive Events in Ring-Closing Metathesis Using Ruthenium Catalysts
journal, June 2010

  • Stewart, Ian C.; Keitz, Benjamin K.; Kuhn, Kevin M.
  • Journal of the American Chemical Society, Vol. 132, Issue 25
  • DOI: 10.1021/ja1029045

Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs)
journal, April 2007

  • Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste
  • Angewandte Chemie International Edition, Vol. 46, Issue 16
  • DOI: 10.1002/anie.200605083

Decomposition of Ruthenium Olefin Metathesis Catalysts
journal, June 2007

  • Hong, Soon Hyeok; Wenzel, Anna G.; Salguero, Tina T.
  • Journal of the American Chemical Society, Vol. 129, Issue 25
  • DOI: 10.1021/ja0713577

Stable Cyclic (Alkyl)(Amino)Carbenes as Rigid or Flexible, Bulky, Electron-Rich Ligands for Transition-Metal Catalysts: A Quaternary Carbon Atom Makes the Difference
journal, September 2005

  • Lavallo, Vincent; Canac, Yves; Präsang, Carsten
  • Angewandte Chemie International Edition, Vol. 44, Issue 35, p. 5705-5709
  • DOI: 10.1002/anie.200501841

Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
journal, February 2008

  • Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik
  • Organometallics, Vol. 27, Issue 4
  • DOI: 10.1021/om7008028

31 P NMR Chemical Shifts of Carbene-Phosphinidene Adducts as an Indicator of the π-Accepting Properties of Carbenes
journal, February 2013

  • Back, Olivier; Henry-Ellinger, Martin; Martin, Caleb D.
  • Angewandte Chemie, Vol. 125, Issue 10
  • DOI: 10.1002/ange.201209109

The Development of L 2 X 2 RuCHR Olefin Metathesis Catalysts:  An Organometallic Success Story
journal, January 2001

  • Trnka, Tina M.; Grubbs, Robert H.
  • Accounts of Chemical Research, Vol. 34, Issue 1
  • DOI: 10.1021/ar000114f

Ruthenium-Based Olefin Metathesis Catalysts Bearing N -Heterocyclic Carbene Ligands
journal, August 2009

  • Samojłowicz, Cezary; Bieniek, Michał; Grela, Karol
  • Chemical Reviews, Vol. 109, Issue 8
  • DOI: 10.1021/cr800524f

Key processes in ruthenium-catalysed olefin metathesis
journal, January 2014

  • Nelson, David J.; Manzini, Simone; Urbina-Blanco, César A.
  • Chemical Communications, Vol. 50, Issue 72
  • DOI: 10.1039/C4CC02515F

Renewable linear alpha olefins by selective ethenolysis of decarboxylated unsaturated fatty acids
journal, June 2012

  • van der Klis, Frits; Le Nôtre, Jérôme; Blaauw, Rolf
  • European Journal of Lipid Science and Technology, Vol. 114, Issue 8
  • DOI: 10.1002/ejlt.201200024

Ethenolysis Reactions Catalyzed by Imido Alkylidene Monoaryloxide Monopyrrolide (MAP) Complexes of Molybdenum
journal, August 2009

  • Marinescu, Smaranda C.; Schrock, Richard R.; Müller, Peter
  • Journal of the American Chemical Society, Vol. 131, Issue 31, p. 10840-10841
  • DOI: 10.1021/ja904786y

Probing the Origin of Degenerate Metathesis Selectivity via Characterization and Dynamics of Ruthenacyclobutanes Containing Variable NHCs
journal, October 2011

  • Keitz, Benjamin K.; Grubbs, Robert H.
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja207252r

Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts
journal, July 2001

  • Sanford, Melanie S.; Love, Jennifer A.; Grubbs, Robert H.
  • Journal of the American Chemical Society, Vol. 123, Issue 27
  • DOI: 10.1021/ja010624k

Synthesis and Reactivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
journal, September 2007

  • Anderson, Donde R.; Lavallo, Vincent; O'Leary, Daniel J.
  • Angewandte Chemie, Vol. 119, Issue 38
  • DOI: 10.1002/ange.200702085

31 P NMR Chemical Shifts of Carbene-Phosphinidene Adducts as an Indicator of the π-Accepting Properties of Carbenes
journal, January 2013

  • Back, Olivier; Henry-Ellinger, Martin; Martin, Caleb D.
  • Angewandte Chemie International Edition, Vol. 52, Issue 10
  • DOI: 10.1002/anie.201209109

Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts
journal, March 2010

  • Vougioukalakis, Georgios C.; Grubbs, Robert H.
  • Chemical Reviews, Vol. 110, Issue 3
  • DOI: 10.1021/cr9002424

Oils and Fats as Renewable Raw Materials in Chemistry
journal, March 2011

  • Biermann, Ursula; Bornscheuer, Uwe; Meier, Michael A. R.
  • Angewandte Chemie International Edition, Vol. 50, Issue 17
  • DOI: 10.1002/anie.201002767

Plant oil renewable resources as green alternatives in polymer science
journal, January 2007

  • Meier, Michael A. R.; Metzger, Jürgen O.; Schubert, Ulrich S.
  • Chemical Society Reviews, Vol. 36, Issue 11
  • DOI: 10.1039/b703294c

Stereoselectivity of Macrocyclic Ring-Closing Olefin Metathesis
journal, July 2000

  • Lee, Choon Woo; Grubbs, Robert H.
  • Organic Letters, Vol. 2, Issue 14
  • DOI: 10.1021/ol006059s

Synthesis of Ruthenium Olefin Metathesis Catalysts with Linear Alkyl Carbene Complexes
journal, March 2005

  • Lehman, Stephen E.; Wagener, Kenneth B.
  • Organometallics, Vol. 24, Issue 7
  • DOI: 10.1021/om049176q

Plant oils: The perfect renewable resource for polymer science?!
journal, May 2011


The E Factor: fifteen years on
journal, January 2007


Molybdän- und Wolframimidoalkylidenkomplexe als effiziente Olefinmetathesekatalysatoren
journal, October 2003


Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007

  • Corma, Avelino; Iborra, Sara; Velty, Alexandra
  • Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
  • DOI: 10.1021/cr050989d

Raffination von Pflanzenölen für die Chemie durch Olefinmetathese
journal, May 2012


Olefinmetathese und mehr
journal, September 2000


Synthesis and Reactivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
journal, September 2007

  • Anderson, Donde R.; Lavallo, Vincent; O'Leary, Daniel J.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7262-7265
  • DOI: 10.1002/anie.200702085

Stabile cyclische Carbene und verwandte Spezies jenseits der Diaminocarbene
journal, September 2010

  • Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy
  • Angewandte Chemie, Vol. 122, Issue 47
  • DOI: 10.1002/ange.201000165

Ruthenium-catalyzed olefin metathesis accelerated by the steric effect of the backbone substituent in cyclic (alkyl)(amino) carbenes
journal, January 2013

  • Zhang, Jun; Song, Shangfei; Wang, Xiao
  • Chemical Communications, Vol. 49, Issue 82
  • DOI: 10.1039/c3cc45823g

Olefin Metathesis and Beyond
journal, September 2000


Application of olefin metathesis in oleochemistry: an example of green chemistry
journal, February 2002


Ruthenium-Based Olefin Metathesis Catalysts Derived from Alkynes
journal, August 2010

  • Lozano-Vila, Ana M.; Monsaert, Stijn; Bajek, Agata
  • Chemical Reviews, Vol. 110, Issue 8
  • DOI: 10.1021/cr900346r

Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs)
journal, April 2007

  • Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste
  • Angewandte Chemie, Vol. 119, Issue 16
  • DOI: 10.1002/ange.200605083

Ruthenium Carbene-Based Olefin Metathesis Initiators:  Catalyst Decomposition and Longevity
journal, September 1999

  • Ulman, Michael; Grubbs, Robert H.
  • The Journal of Organic Chemistry, Vol. 64, Issue 19
  • DOI: 10.1021/jo9908703

Ruthenium vinyl carbene intermediates in enyne metathesis
journal, March 2007


Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin-Metathesis Catalysts
journal, October 2003

  • Schrock, Richard R.; Hoveyda, Amir H.
  • Angewandte Chemie International Edition, Vol. 42, Issue 38, p. 4592-4633
  • DOI: 10.1002/anie.200300576

Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis
journal, May 2011

  • Thomas, Renee M.; Keitz, Benjamin K.; Champagne, Timothy M.
  • Journal of the American Chemical Society, Vol. 133, Issue 19
  • DOI: 10.1021/ja200246e

Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes
journal, September 2010

  • Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy
  • Angewandte Chemie International Edition, Vol. 49, Issue 47
  • DOI: 10.1002/anie.201000165

Metathesis Reactions in Total Synthesis
journal, July 2005

  • Nicolaou, K. C.; Bulger, Paul G.; Sarlah, David
  • Angewandte Chemie International Edition, Vol. 44, Issue 29
  • DOI: 10.1002/anie.200500369

Nature of the Transition Metal–Carbene Bond in Grubbs Olefin Metathesis Catalysts
journal, July 2011

  • Occhipinti, Giovanni; Jensen, Vidar R.
  • Organometallics, Vol. 30, Issue 13
  • DOI: 10.1021/om200181y

High conversion and productive catalyst turnovers in cross-metathesis reactions of natural oils with 2-butene
journal, January 2006

  • Patel, Jim; Mujcinovic, S.; Jackson, W. Roy
  • Green Chemistry, Vol. 8, Issue 5
  • DOI: 10.1039/b600956e

Stereoselectivity of Macrocyclic Ring-Closing Olefin Metathesis
journal, August 2000

  • Lee, Choon Woo; Grubbs, Robert H.
  • Organic Letters, Vol. 2, Issue 16
  • DOI: 10.1021/ol000167x

    Works referencing / citing this record:

    Olefinmetathese und mehr
    journal, September 2000


    Olefin Metathesis and Beyond
    journal, September 2000


    A Ruthenium Catalyst for Olefin Metathesis Featuring an Anti-Bredt N-Heterocyclic Carbene Ligand
    journal, February 2016

    • Martin, David; Marx, Vanessa M.; Grubbs, Robert H.
    • Advanced Synthesis & Catalysis, Vol. 358, Issue 6
    • DOI: 10.1002/adsc.201501140

    Molybdän- und Wolframimidoalkylidenkomplexe als effiziente Olefinmetathesekatalysatoren
    journal, October 2003


    Metathesereaktionen in der Totalsynthese
    journal, July 2005

    • Nicolaou, K. C.; Bulger, Paul G.; Sarlah, David
    • Angewandte Chemie, Vol. 117, Issue 29
    • DOI: 10.1002/ange.200500369

    Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs)
    journal, April 2007

    • Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste
    • Angewandte Chemie, Vol. 119, Issue 16
    • DOI: 10.1002/ange.200605083

    Synthesis and Reactivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
    journal, September 2007

    • Anderson, Donde R.; Lavallo, Vincent; O'Leary, Daniel J.
    • Angewandte Chemie, Vol. 119, Issue 38
    • DOI: 10.1002/ange.200702085

    Stabile cyclische Carbene und verwandte Spezies jenseits der Diaminocarbene
    journal, September 2010

    • Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy
    • Angewandte Chemie, Vol. 122, Issue 47
    • DOI: 10.1002/ange.201000165

    Fette und Öle als nachwachsende Rohstoffe in der Chemie
    journal, March 2011

    • Biermann, Ursula; Bornscheuer, Uwe; Meier, Michael A. R.
    • Angewandte Chemie, Vol. 123, Issue 17
    • DOI: 10.1002/ange.201002767

    Raffination von Pflanzenölen für die Chemie durch Olefinmetathese
    journal, May 2012


    31 P NMR Chemical Shifts of Carbene-Phosphinidene Adducts as an Indicator of the π-Accepting Properties of Carbenes
    journal, February 2013

    • Back, Olivier; Henry-Ellinger, Martin; Martin, Caleb D.
    • Angewandte Chemie, Vol. 125, Issue 10
    • DOI: 10.1002/ange.201209109

    Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin-Metathesis Catalysts
    journal, October 2003

    • Schrock, Richard R.; Hoveyda, Amir H.
    • Angewandte Chemie International Edition, Vol. 42, Issue 38, p. 4592-4633
    • DOI: 10.1002/anie.200300576

    Metathesis Reactions in Total Synthesis
    journal, July 2005

    • Nicolaou, K. C.; Bulger, Paul G.; Sarlah, David
    • Angewandte Chemie International Edition, Vol. 44, Issue 29
    • DOI: 10.1002/anie.200500369

    Stable Cyclic (Alkyl)(Amino)Carbenes as Rigid or Flexible, Bulky, Electron-Rich Ligands for Transition-Metal Catalysts: A Quaternary Carbon Atom Makes the Difference
    journal, September 2005

    • Lavallo, Vincent; Canac, Yves; Präsang, Carsten
    • Angewandte Chemie International Edition, Vol. 44, Issue 35, p. 5705-5709
    • DOI: 10.1002/anie.200501841

    Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs)
    journal, April 2007

    • Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste
    • Angewandte Chemie International Edition, Vol. 46, Issue 16
    • DOI: 10.1002/anie.200605083

    Synthesis and Reactivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
    journal, September 2007

    • Anderson, Donde R.; Lavallo, Vincent; O'Leary, Daniel J.
    • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7262-7265
    • DOI: 10.1002/anie.200702085

    Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes
    journal, September 2010

    • Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy
    • Angewandte Chemie International Edition, Vol. 49, Issue 47
    • DOI: 10.1002/anie.201000165

    Oils and Fats as Renewable Raw Materials in Chemistry
    journal, March 2011

    • Biermann, Ursula; Bornscheuer, Uwe; Meier, Michael A. R.
    • Angewandte Chemie International Edition, Vol. 50, Issue 17
    • DOI: 10.1002/anie.201002767

    Refining of Plant Oils to Chemicals by Olefin Metathesis
    journal, May 2012

    • Chikkali, Samir; Mecking, Stefan
    • Angewandte Chemie International Edition, Vol. 51, Issue 24
    • DOI: 10.1002/anie.201107645

    31 P NMR Chemical Shifts of Carbene-Phosphinidene Adducts as an Indicator of the π-Accepting Properties of Carbenes
    journal, January 2013

    • Back, Olivier; Henry-Ellinger, Martin; Martin, Caleb D.
    • Angewandte Chemie International Edition, Vol. 52, Issue 10
    • DOI: 10.1002/anie.201209109

    Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis
    journal, March 2016

    • Pucino, Margherita; Mougel, Victor; Schowner, Roman
    • Angewandte Chemie International Edition, Vol. 55, Issue 13
    • DOI: 10.1002/anie.201510678

    Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis
    journal, December 2016

    • Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A.
    • Angewandte Chemie International Edition, Vol. 56, Issue 4
    • DOI: 10.1002/anie.201609009

    First Neutral and Cationic Tungsten Imido Alkylidene N -Heterocyclic Carbene Complexes
    journal, June 2017


    Useful Products from Complex Starting Materials: Common Chemicals from Biomass Feedstocks
    journal, April 2010

    • Marshall, Amanda-Lynn; Alaimo, Peter J.
    • Chemistry - A European Journal, Vol. 16, Issue 17
    • DOI: 10.1002/chem.200903028

    Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica
    journal, August 2015

    • Sen, Suman; Schowner, Roman; Imbrich, Dominik A.
    • Chemistry - A European Journal, Vol. 21, Issue 39
    • DOI: 10.1002/chem.201501615

    A Cyclic Alkyl(amino)carbene as Two-Atom π-Chromophore Leading to the First Phosphorescent Linear Cu I Complexes
    journal, January 2017

    • Gernert, Markus; Müller, Ulrich; Haehnel, Martin
    • Chemistry - A European Journal, Vol. 23, Issue 9
    • DOI: 10.1002/chem.201605412

    Renewable linear alpha olefins by selective ethenolysis of decarboxylated unsaturated fatty acids
    journal, June 2012

    • van der Klis, Frits; Le Nôtre, Jérôme; Blaauw, Rolf
    • European Journal of Lipid Science and Technology, Vol. 114, Issue 8
    • DOI: 10.1002/ejlt.201200024

    A Highly Efficient Olefin Metathesis Process for the Synthesis of Terminal Alkenes from Fatty Acid Esters
    journal, June 2012


    Ruthenium vinyl carbene intermediates in enyne metathesis
    journal, March 2007


    Plant oils: The perfect renewable resource for polymer science?!
    journal, May 2011


    The Development of L 2 X 2 RuCHR Olefin Metathesis Catalysts:  An Organometallic Success Story
    journal, January 2001

    • Trnka, Tina M.; Grubbs, Robert H.
    • Accounts of Chemical Research, Vol. 34, Issue 1
    • DOI: 10.1021/ar000114f

    High Oxidation State Multiple Metal−Carbon Bonds
    journal, January 2002


    Chemical Routes for the Transformation of Biomass into Chemicals
    journal, June 2007

    • Corma, Avelino; Iborra, Sara; Velty, Alexandra
    • Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
    • DOI: 10.1021/cr050989d

    Ruthenium-Based Olefin Metathesis Catalysts Bearing N -Heterocyclic Carbene Ligands
    journal, August 2009

    • Samojłowicz, Cezary; Bieniek, Michał; Grela, Karol
    • Chemical Reviews, Vol. 109, Issue 8
    • DOI: 10.1021/cr800524f

    Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts
    journal, March 2010

    • Vougioukalakis, Georgios C.; Grubbs, Robert H.
    • Chemical Reviews, Vol. 110, Issue 3
    • DOI: 10.1021/cr9002424

    Ruthenium-Based Olefin Metathesis Catalysts Derived from Alkynes
    journal, August 2010

    • Lozano-Vila, Ana M.; Monsaert, Stijn; Bajek, Agata
    • Chemical Reviews, Vol. 110, Issue 8
    • DOI: 10.1021/cr900346r

    Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts
    journal, July 2001

    • Sanford, Melanie S.; Love, Jennifer A.; Grubbs, Robert H.
    • Journal of the American Chemical Society, Vol. 123, Issue 27
    • DOI: 10.1021/ja010624k

    Decomposition of Ruthenium Olefin Metathesis Catalysts
    journal, June 2007

    • Hong, Soon Hyeok; Wenzel, Anna G.; Salguero, Tina T.
    • Journal of the American Chemical Society, Vol. 129, Issue 25
    • DOI: 10.1021/ja0713577

    Nonproductive Events in Ring-Closing Metathesis Using Ruthenium Catalysts
    journal, June 2010

    • Stewart, Ian C.; Keitz, Benjamin K.; Kuhn, Kevin M.
    • Journal of the American Chemical Society, Vol. 132, Issue 25
    • DOI: 10.1021/ja1029045

    Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis
    journal, May 2011

    • Thomas, Renee M.; Keitz, Benjamin K.; Champagne, Timothy M.
    • Journal of the American Chemical Society, Vol. 133, Issue 19
    • DOI: 10.1021/ja200246e

    Probing the Origin of Degenerate Metathesis Selectivity via Characterization and Dynamics of Ruthenacyclobutanes Containing Variable NHCs
    journal, October 2011

    • Keitz, Benjamin K.; Grubbs, Robert H.
    • Journal of the American Chemical Society, Vol. 133, Issue 40
    • DOI: 10.1021/ja207252r

    Ethenolysis Reactions Catalyzed by Imido Alkylidene Monoaryloxide Monopyrrolide (MAP) Complexes of Molybdenum
    journal, August 2009

    • Marinescu, Smaranda C.; Schrock, Richard R.; Müller, Peter
    • Journal of the American Chemical Society, Vol. 131, Issue 31, p. 10840-10841
    • DOI: 10.1021/ja904786y

    Ruthenium Carbene-Based Olefin Metathesis Initiators:  Catalyst Decomposition and Longevity
    journal, September 1999

    • Ulman, Michael; Grubbs, Robert H.
    • The Journal of Organic Chemistry, Vol. 64, Issue 19
    • DOI: 10.1021/jo9908703

    Stereoselectivity of Macrocyclic Ring-Closing Olefin Metathesis
    journal, July 2000

    • Lee, Choon Woo; Grubbs, Robert H.
    • Organic Letters, Vol. 2, Issue 14
    • DOI: 10.1021/ol006059s

    Synthesis of Ruthenium Olefin Metathesis Catalysts with Linear Alkyl Carbene Complexes
    journal, March 2005

    • Lehman, Stephen E.; Wagener, Kenneth B.
    • Organometallics, Vol. 24, Issue 7
    • DOI: 10.1021/om049176q

    Nature of the Transition Metal–Carbene Bond in Grubbs Olefin Metathesis Catalysts
    journal, July 2011

    • Occhipinti, Giovanni; Jensen, Vidar R.
    • Organometallics, Vol. 30, Issue 13
    • DOI: 10.1021/om200181y

    Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
    journal, February 2008

    • Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik
    • Organometallics, Vol. 27, Issue 4
    • DOI: 10.1021/om7008028

    Application of olefin metathesis in oleochemistry: an example of green chemistry
    journal, February 2002


    High conversion and productive catalyst turnovers in cross-metathesis reactions of natural oils with 2-butene
    journal, January 2006

    • Patel, Jim; Mujcinovic, S.; Jackson, W. Roy
    • Green Chemistry, Vol. 8, Issue 5
    • DOI: 10.1039/b600956e

    Plant oil renewable resources as green alternatives in polymer science
    journal, January 2007

    • Meier, Michael A. R.; Metzger, Jürgen O.; Schubert, Ulrich S.
    • Chemical Society Reviews, Vol. 36, Issue 11
    • DOI: 10.1039/b703294c

    The E Factor: fifteen years on
    journal, January 2007


    Ruthenium-catalyzed olefin metathesis accelerated by the steric effect of the backbone substituent in cyclic (alkyl)(amino) carbenes
    journal, January 2013

    • Zhang, Jun; Song, Shangfei; Wang, Xiao
    • Chemical Communications, Vol. 49, Issue 82
    • DOI: 10.1039/c3cc45823g

    Key processes in ruthenium-catalysed olefin metathesis
    journal, January 2014

    • Nelson, David J.; Manzini, Simone; Urbina-Blanco, César A.
    • Chemical Communications, Vol. 50, Issue 72
    • DOI: 10.1039/c4cc02515f

    Neutral Fe( iv ) alkylidenes, including some that bind dinitrogen
    journal, January 2016

    • Lindley, Brian M.; Jacobs, Brian P.; MacMillan, Samantha N.
    • Chemical Communications, Vol. 52, Issue 20
    • DOI: 10.1039/c5cc08825a

    Fe( iv ) alkylidenes via protonation of Fe( ii ) vinyl chelates and a comparative Mössbauer spectroscopic study
    journal, January 2015

    • Lindley, Brian M.; Swidan, Ala'aeddeen; Lobkovsky, Emil B.
    • Chemical Science, Vol. 6, Issue 8
    • DOI: 10.1039/c5sc01268f

    Synthesis and catalytic activity of ruthenium indenylidene complexes bearing unsymmetrical NHC containing a heteroaromatic moiety
    journal, January 2016

    • Smoleń, Michał; Kośnik, Wioletta; Loska, Rafał
    • RSC Advances, Vol. 6, Issue 80
    • DOI: 10.1039/c6ra18210k

    Stable ruthenium olefin metathesis catalysts bearing symmetrical NHC ligands with primary and secondary N -alkyl groups
    journal, January 2018

    • Ambrosio, Chiara; Paradiso, Veronica; Costabile, Chiara
    • Dalton Transactions, Vol. 47, Issue 18
    • DOI: 10.1039/c8dt00619a

    The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis
    journal, January 2019

    • Pichon, Delphine; Soleilhavoup, Michele; Morvan, Jennifer
    • Chemical Science, Vol. 10, Issue 33
    • DOI: 10.1039/c9sc02810b

    A Ruthenium Catalyst for Olefin Metathesis Featuring an Anti-Bredt N-Heterocyclic Carbene Ligand
    journal, February 2016

    • Martin, David; Marx, Vanessa M.; Grubbs, Robert H.
    • Advanced Synthesis & Catalysis, Vol. 358, Issue 6
    • DOI: 10.1002/adsc.201501140

    Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis
    journal, March 2016

    • Pucino, Margherita; Mougel, Victor; Schowner, Roman
    • Angewandte Chemie, Vol. 128, Issue 13
    • DOI: 10.1002/ange.201510678

    Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis
    journal, December 2016

    • Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A.
    • Angewandte Chemie International Edition, Vol. 56, Issue 4
    • DOI: 10.1002/anie.201609009

    First Neutral and Cationic Tungsten Imido Alkylidene N -Heterocyclic Carbene Complexes
    journal, June 2017


    Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica
    journal, August 2015

    • Sen, Suman; Schowner, Roman; Imbrich, Dominik A.
    • Chemistry - A European Journal, Vol. 21, Issue 39
    • DOI: 10.1002/chem.201501615

    A Cyclic Alkyl(amino)carbene as Two-Atom π-Chromophore Leading to the First Phosphorescent Linear Cu I Complexes
    journal, January 2017

    • Gernert, Markus; Müller, Ulrich; Haehnel, Martin
    • Chemistry - A European Journal, Vol. 23, Issue 9
    • DOI: 10.1002/chem.201605412

    Neutral Fe( iv ) alkylidenes, including some that bind dinitrogen
    journal, January 2016

    • Lindley, Brian M.; Jacobs, Brian P.; MacMillan, Samantha N.
    • Chemical Communications, Vol. 52, Issue 20
    • DOI: 10.1039/c5cc08825a

    Fe( iv ) alkylidenes via protonation of Fe( ii ) vinyl chelates and a comparative Mössbauer spectroscopic study
    journal, January 2015

    • Lindley, Brian M.; Swidan, Ala'aeddeen; Lobkovsky, Emil B.
    • Chemical Science, Vol. 6, Issue 8
    • DOI: 10.1039/c5sc01268f

    Synthesis and catalytic activity of ruthenium indenylidene complexes bearing unsymmetrical NHC containing a heteroaromatic moiety
    journal, January 2016

    • Smoleń, Michał; Kośnik, Wioletta; Loska, Rafał
    • RSC Advances, Vol. 6, Issue 80
    • DOI: 10.1039/c6ra18210k

    Stable ruthenium olefin metathesis catalysts bearing symmetrical NHC ligands with primary and secondary N -alkyl groups
    journal, January 2018

    • Ambrosio, Chiara; Paradiso, Veronica; Costabile, Chiara
    • Dalton Transactions, Vol. 47, Issue 18
    • DOI: 10.1039/c8dt00619a

    The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis
    journal, January 2019

    • Pichon, Delphine; Soleilhavoup, Michele; Morvan, Jennifer
    • Chemical Science, Vol. 10, Issue 33
    • DOI: 10.1039/c9sc02810b

    Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis
    journal, March 2016

    • Pucino, Margherita; Mougel, Victor; Schowner, Roman
    • Angewandte Chemie International Edition, Vol. 55, Issue 13
    • DOI: 10.1002/anie.201510678

    Cyclische Alkylaminocarbene (CAACs): Neues von guten Bekannten
    journal, June 2017

    • Melaimi, Mohand; Jazzar, Rodolphe; Soleilhavoup, Michèle
    • Angewandte Chemie, Vol. 129, Issue 34
    • DOI: 10.1002/ange.201702148

    Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments
    journal, June 2017

    • Melaimi, Mohand; Jazzar, Rodolphe; Soleilhavoup, Michèle
    • Angewandte Chemie International Edition, Vol. 56, Issue 34
    • DOI: 10.1002/anie.201702148

    Direct and Tandem Routes for the Copolymerization of Ethylene with Polar Functionalized Internal Olefins
    journal, December 2019

    • Chen, Min; Chen, Changle
    • Angewandte Chemie International Edition, Vol. 59, Issue 3
    • DOI: 10.1002/anie.201913088

    One‐pot Synthesis of 1,3‐Butadiene and 1,6‐Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions
    journal, September 2018

    • Turczel, Gábor; Kovács, Ervin; Csizmadia, Eszter
    • ChemCatChem, Vol. 10, Issue 21
    • DOI: 10.1002/cctc.201801088

    A Gentler Touch: Synthesis of Modern Ruthenium Olefin Metathesis Catalysts Sustained by Mechanical Force
    journal, March 2019

    • Mukherjee, Nirmalya; Marczyk, Anna; Szczepaniak, Grzegorz
    • ChemCatChem, Vol. 11, Issue 21
    • DOI: 10.1002/cctc.201901444

    Ethenolysis: A Green Catalytic Tool to Cleave Carbon-Carbon Double Bonds
    journal, June 2016

    • Bidange, Johan; Fischmeister, Cédric; Bruneau, Christian
    • Chemistry - A European Journal, Vol. 22, Issue 35
    • DOI: 10.1002/chem.201601052

    Acid‐Assisted Direct Olefin Metathesis of Unprotected Carbohydrates in Water
    journal, October 2019

    • Timmer, Brian J. J.; Ramström, Olof
    • Chemistry – A European Journal, Vol. 25, Issue 63
    • DOI: 10.1002/chem.201903155

    In a Quest for Selectivity Paired with Activity: A Ruthenium Olefin Metathesis Catalyst Bearing an Unsymmetrical Phenanthrene‐Based N‐Heterocyclic Carbene
    journal, March 2020

    • Dąbrowski, Michał; Wyrębek, Przemysław; Trzybiński, Damian
    • Chemistry – A European Journal, Vol. 26, Issue 17
    • DOI: 10.1002/chem.201904549

    Me CAAC=N : A Cyclic (Alkyl)(Amino)Carbene Imino Ligand
    journal, January 2020

    • Goettel, James T.; Gao, Haopeng; Dotzauer, Simon
    • Chemistry – A European Journal, Vol. 26, Issue 5
    • DOI: 10.1002/chem.201904715

    Remarkably Efficient Microwave-Assisted Cross-Metathesis of Lipids under Solvent-Free Conditions
    journal, May 2017


    Preparation of Musk-Smelling Macrocyclic Lactones from Biomass: Looking for the Optimal Substrate Combination
    journal, August 2018

    • Sytniczuk, Adrian; Leszczyńska, Agnieszka; Kajetanowicz, Anna
    • ChemSusChem, Vol. 11, Issue 18
    • DOI: 10.1002/cssc.201801463

    Merrifield resin-assisted routes to second-generation catalysts for olefin metathesis
    journal, January 2018

    • Nascimento, Daniel L.; Davy, Emma C.; Fogg, Deryn E.
    • Catalysis Science & Technology, Vol. 8, Issue 6
    • DOI: 10.1039/c7cy02278f

    Highly efficient and time economical purification of olefin metathesis products from metal residues using an isocyanide scavenger
    journal, January 2018

    • Szczepaniak, Grzegorz; Ruszczyńska, Anna; Kosiński, Krzysztof
    • Green Chemistry, Vol. 20, Issue 6
    • DOI: 10.1039/c7gc03324a

    Recent advances in ruthenium-based olefin metathesis
    journal, January 2018

    • Ogba, O. M.; Warner, N. C.; O’Leary, D. J.
    • Chemical Society Reviews, Vol. 47, Issue 12
    • DOI: 10.1039/c8cs00027a

    Transformations of terpenes and terpenoids via carbon–carbon double bond metathesis
    journal, January 2018

    • Bruneau, Christian; Fischmeister, Cédric; Mandelli, Dalmo
    • Catalysis Science & Technology, Vol. 8, Issue 16
    • DOI: 10.1039/c8cy01152d

    Techno-economic analysis and life-cycle greenhouse gas mitigation cost of five routes to bio-jet fuel blendstocks
    journal, January 2019

    • Baral, Nawa Raj; Kavvada, Olga; Mendez-Perez, Daniel
    • Energy & Environmental Science, Vol. 12, Issue 3
    • DOI: 10.1039/c8ee03266a

    Recent progress on donor and donor–donor carbenes
    journal, January 2020

    • Zhu, Dong; Chen, Lianfen; Fan, Hanlin
    • Chemical Society Reviews, Vol. 49, Issue 3
    • DOI: 10.1039/c9cs00542k

    Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity
    journal, January 2020

    • Wang, Hai-Xu; Wan, Qingyun; Low, Kam-Hung
    • Chemical Science, Vol. 11, Issue 8
    • DOI: 10.1039/c9sc05432d

    Seed-specific RNAi in safflower generates a superhigh oleic oil with extended oxidative stability
    journal, April 2018

    • Wood, Craig C.; Okada, Shoko; Taylor, Matthew C.
    • Plant Biotechnology Journal, Vol. 16, Issue 10
    • DOI: 10.1111/pbi.12915

    Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions
    journal, January 2015

    • Tracz, Andrzej; Matczak, Mateusz; Urbaniak, Katarzyna
    • Beilstein Journal of Organic Chemistry, Vol. 11
    • DOI: 10.3762/bjoc.11.198

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.