Light- and Thermal-Activated Olefin Metathesis of Hindered Substrates

Efficient light- and thermal-activated metathesis reactions of tetra-substituted olefins were obtained by the S-chelated ruthenium precatalyst Tol-SCF3. Its reactivity in a series of benchmark olefin metathesis reactions was compared to previously reported Mes-SCF3 and a novel sterically congested S-chelated complex, Dipp-SCF3. Tol-SCF3 is thus the first latent catalyst proven to be capable of promoting olefin metathesis of demanding substrates upon light stimulation at room temperature.

[1]  David J Nelson,et al.  Quantifying and understanding the steric properties of N-heterocyclic carbenes. , 2017, Chemical communications.

[2]  Celia Arnaud,et al.  Attacking asbestos from all angles , 2016 .

[3]  Malte S. Mikus,et al.  Pentacoordinate Ruthenium(II) Catecholthiolate and Mercaptophenolate Catalysts for Olefin Metathesis: Anionic Ligand Exchange and Ease of Initiation , 2016 .

[4]  Xiao He,et al.  Correction: MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions , 2016, Chemical science.

[5]  N. G. Lemcoff,et al.  Cross-linked ROMP polymers based on odourless dicyclopentadiene derivatives , 2016 .

[6]  D. Stephan,et al.  Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis. , 2016, Dalton transactions.

[7]  C. Bielawski,et al.  Switchable Polymerization Catalysts. , 2016, Chemical reviews.

[8]  I. Goldberg,et al.  A Light-Activated Olefin Metathesis Catalyst Equipped with a Chromatic Orthogonal Self-Destruct Function. , 2016, Angewandte Chemie.

[9]  L. Cavallo,et al.  Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators , 2015 .

[10]  N. G. Lemcoff,et al.  Regioselective chromatic orthogonality with light-activated metathesis catalysts. , 2015, Angewandte Chemie.

[11]  L. Cavallo,et al.  A theoretical view on the thermodynamic cis–trans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts , 2015, Monatshefte für Chemie - Chemical Monthly.

[12]  P. Longo,et al.  Ruthenium Olefin Metathesis Catalysts with Frozen NHC Ligand Conformations , 2014 .

[13]  M. Barbasiewicz,et al.  Mechanistic studies of Hoveyda-Grubbs metathesis catalysts bearing S-, Br-, I-, and N-coordinating naphthalene ligands. , 2014, Chemistry.

[14]  D. Stephan,et al.  A Tridentate-Dithiolate Ruthenium Alkylidene Complex: An Olefin Metathesis Catalyst Activated by BCl3 , 2013 .

[15]  A. Hoveyda,et al.  Readily accessible and easily modifiable Ru-based catalysts for efficient and Z-selective ring-opening metathesis polymerization and ring-opening/cross-metathesis. , 2013, Journal of the American Chemical Society.

[16]  A. Zieliński,et al.  Stable ruthenium indenylidene complexes with a sterically reduced NHC ligand. , 2013, Chemical communications.

[17]  V. R. Jensen,et al.  Simple and highly Z-selective ruthenium-based olefin metathesis catalyst. , 2013, Journal of the American Chemical Society.

[18]  R. Grubbs,et al.  Decomposition pathways of Z-selective ruthenium metathesis catalysts. , 2012, Journal of the American Chemical Society.

[19]  H. Plenio,et al.  On the mechanism of the initiation reaction in Grubbs-Hoveyda complexes. , 2012, Journal of the American Chemical Society.

[20]  A. Slawin,et al.  An unusual cationic Ru(II) indenylidene complex and its Ru(III) derivative--efficient catalysts for high temperature olefin metathesis reactions. , 2012, Chemical communications.

[21]  L. Cavallo,et al.  A computational perspective of olefins metathesis catalyzed by N-heterocyclic carbene ruthenium (pre)catalysts , 2011 .

[22]  I. Goldberg,et al.  Widening the Latency Gap in Chelated Ruthenium Olefin Metathesis Catalysts , 2011 .

[23]  I. Goldberg,et al.  Ligand Isomerization in Sulfur-Chelated Ruthenium Benzylidenes , 2011 .

[24]  Y. Vidavsky,et al.  Light-induced olefin metathesis , 2010, Beilstein journal of organic chemistry.

[25]  A. Slawin,et al.  Mixed N-heterocyclic carbene/phosphite ruthenium complexes: towards a new generation of olefin metathesis catalysts. , 2010, Chemical communications.

[26]  I. Goldberg,et al.  Latent and Switchable Olefin Metathesis Catalysts , 2010 .

[27]  H. Plenio,et al.  Synthesis and RCM Activity of [(NHC)(NHCewg)RuCl2(3-phenylindenylid-1-ene)] Complexes , 2010 .

[28]  Brice Stenne,et al.  Desymmetrizations forming tetrasubstituted olefins using enantioselective olefin metathesis. , 2010, Organic letters.

[29]  F. Verpoort,et al.  Latent olefin metathesis catalysts. , 2009, Chemical Society reviews.

[30]  P. Longo,et al.  Influence of syn and anti Configurations of NHC Backbone on Ru-Catalyzed Olefin Metathesis , 2009 .

[31]  I. Goldberg,et al.  Photoactivation of Ruthenium Olefin Metathesis Initiators , 2009 .

[32]  R. Grubbs,et al.  Effects of NHC-backbone substitution on efficiency in ruthenium-based olefin metathesis. , 2009, Journal of the American Chemical Society.

[33]  César A. Urbina-Blanco,et al.  Indenylidene Ruthenium Complex Bearing a Sterically Demanding NHC Ligand: An Efficient Catalyst for Olefin Metathesis at Room Temperature , 2009 .

[34]  Ian C. Stewart,et al.  Conformations of N-heterocyclic carbene ligands in ruthenium complexes relevant to olefin metathesis. , 2009, Journal of the American Chemical Society.

[35]  Anna Grela Initiation at Snails Pace: Design and Applications of Latent Olefin Metathesis Catalysts Featuring Chelating Alkylidene Ligands , 2008 .

[36]  I. Goldberg,et al.  A Thermally Switchable Latent Ruthenium Olefin Metathesis Catalyst , 2008 .

[37]  Ian C. Stewart,et al.  Increased efficiency in cross-metathesis reactions of sterically hindered olefins. , 2008, Organic letters.

[38]  S. Blechert,et al.  Deactivation of ruthenium olefin metathesis catalysts through intramolecular carbene-arene bond formation. , 2007, Angewandte Chemie.

[39]  R. Grubbs,et al.  Highly efficient ruthenium catalysts for the formation of tetrasubstituted olefins via ring-closing metathesis. , 2007, Organic letters.

[40]  Anatoly Chlenov,et al.  Ruthenium-catalyzed ring-closing metathesis to form tetrasubstituted olefins. , 2007, Organic letters.

[41]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[42]  L. Cavallo,et al.  Origin of enantioselectivity in the asymmetric Ru-catalyzed metathesis of olefins. , 2004, Journal of the American Chemical Society.

[43]  K. Wagener,et al.  Metathesis Activity and Stability of New Generation Ruthenium Polymerization Catalysts , 2003 .

[44]  F. Stelzer,et al.  Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands. , 2001, Chemistry.