The Impact of Water On Ru-Catalyzed Olefin Metathesis (Article Presentation)
The Impact of Water On Ru-Catalyzed Olefin Metathesis (Article Presentation)
The Impact of Water On Ru-Catalyzed Olefin Metathesis (Article Presentation)
pubs.acs.org/acscatalysis Letter
Chart 1. Olefin Metathesis Catalysts Discussed product, as with any conformationally flexible diene.24,25 For 1,
in which the ester functionality confers the sole conformational
bias toward cyclization,26 a diene concentration of ≤5 mM is
required.24 At catalyst loadings of 0.05 mol %, this translates
into 2.5 μM Ru: even low concentrations of water are thus
stoichiometrically significant.
In dry toluene, mRCM of 1 reached 83% yield within 0.5 h
at RT (Figure 1a). Addition of 0.01% waterthat is, 100 ppm
by volumecaused a ca. 60% drop in yield. At higher
proportions of water (0.1 or 1% v/v), mRCM failed, signifying
near-complete catalyst decomposition.
As shown in Figure 1b, the Grela catalyst Ru-2 is
decomposed to a lesser extent, affording 30% mRCM in the
presence of 0.1% v/v water (vs 87% mRCM in dry toluene).27
More robust is the iodide analogue Ru-3. Watersomewhat
unexpectedlyis emerging as a much more aggressive agent
than O2 in Ru-catalyzed olefin metathesis,28 and this higher
water-tolerance is thus presumed to be key to the strong
performance of Ru-3 in aerobic metathesis.29 One probable
contributor to improved tolerance is the limited capacity of
Ru-3 to enter into hydrogen-bonding interactions with water.
ROH···Cl−Ru interactions have been reported for related
metathesis catalysts,30,31 and the higher water-sensitivity of Ru-
1 vs Ru-2 is consistent with stronger H-bonding to a dangling
NH2 functionality.
To assess the potential impact of water on E/Z selectivity,
two Z-selective catalysts (Ru-6, Ru-5) were also examined.
Their lower reactivity necessitated use of elevated temper-
atures (60 °C) and higher catalyst loadings. For Ru-5, only
17% mRCM was observed even with 5 mol % catalyst: added
practice, water is a ubiquitous, little-regarded contaminant. It water had no impact, probably because only a small proportion
thus seemed plausible that water-induced decomposition might of catalyst had initiated.32 Ru-6 afforded 64% mRCM in the
contribute to the inconsistent performance of Ru-1. anhydrous reaction (0.5 mol % Ru), and 25% in the presence
To probe this point, we examined the impact of water on of water. Of note, water had a negligible impact on Z-selectivity
mRCM of 1 (Figure 1a).23 This reaction affords the olfactory (Ru-6, 85%; Ru-5, 70%). We infer that decomposed catalyst
lactone 2 via a concentration-dependent ring−chain equili- does not promote E/Z isomerization, at least for Ru-6.
brium.24 High dilutions are essential to favor the cyclic Strikingly, however, water significantly accelerated positional
isomerization in the self-metathesis of allylbenzene 3 (Figure
2a). Terminal phenylpropenes are notoriously susceptible to
isomerization to the conjugated β-methylstyrenes.16c For Ru-6,
8% isomerization was observed for the anhydrous reaction, vs
75% with 1% H2O present. In comparison, Ru-3 showed more
isomerization in the anhydrous reaction, but added water
affected primarily conversions.
A second, more demanding intermolecular metathesis
reaction was also examined. In the cross-metathesis of anethole
6 with methyl acrylate 7 (Figure 2b), a ca. 30% drop in
productivity was observed for Ru-3 in the presence of 1% H2O.
To assess whether the negative impact of water is limited to
relatively challenging reactions, we turned to RCM of diethyl
diallylmalonate 9 (Figure 3). Diene 9 sets a notoriously low
bar for olefin metathesis activity: the extreme facility with
which it undergoes RCM makes it a correspondingly aggressive
test for the impact of water. Here, in addition to the catalysts
examined above, we include benzylidene, indenylidene, NHC,
and CAAC catalysts.29,34−36 Initial experiments were con-
ducted at 0.005 mol % catalyst (50 ppm vs substrate), to
enable “anhydrous” TONs in the thousands even for less active
catalysts, without masking decomposition.37
Shown in Figure 3a are TONs at 2 h, at which point
Figure 1. Impact of water on mRCM. (a) For Ru-1 at 0.5 h. (b) For conversions in the presence of water plateau (Figure S1) for all
various catalysts at 2 h (except Ru-6: 24 h). *Ru-5, Ru-6: 60 °C, 0.01 but Ru-7 and Ru-10. Notwithstanding the ease of this RCM
atm.33 For tabulated data, see Table S1. reaction, yields decreased sharply in the presence of 1% H2O
894 https://dx.doi.org/10.1021/acscatal.0c04279
ACS Catal. 2021, 11, 893−899
ACS Catalysis pubs.acs.org/acscatalysis Letter
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pubs.acs.org/acscatalysis Letter
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.0c04279.
Experimental and computational details, numerical data
for Figures 1−4 (PDF)
Computed xyz coordinates and energies (ZIP)
■ AUTHOR INFORMATION
Corresponding Authors
Deryn E. Fogg − Center for Catalysis Research & Innovation,
and Department of Chemistry and Biomolecular Sciences,
University of Ottawa, Ottawa, Ontario K1N 6N57, Canada;
Department of Chemistry, University of Bergen, N-5007
Bergen, Norway; orcid.org/0000-0002-4528-1139;
Email: [email protected], [email protected]
Carine Michel − Univ. Lyon, ENS de Lyon, CNRS UMR
5182, Université Claude Bernard Lyon 1, Laboratorie de
Chimie, F-69342 Lyon, France; orcid.org/0000-0002-
4501-7194; Email: [email protected]
Figure 4. (a) Impact of 1 H2O on the free energies required to adopt Authors
the incipient (“pre-cyclic”) conformation for 1 and 9. (b)
Destabilization of precyclic conformations by H-bonded water. C···
Christian O. Blanco − Center for Catalysis Research &
C distances: 3.72 Å (1); 4.21 Å (9). Innovation, and Department of Chemistry and Biomolecular
Sciences, University of Ottawa, Ottawa, Ontario K1N 6N57,
Canada
Joshua Sims − Univ. Lyon, ENS de Lyon, CNRS UMR 5182,
on the cyclization kinetics. Macrocyclization of 1 is impeded by Université Claude Bernard Lyon 1, Laboratorie de Chimie, F-
location of the water molecule in the middle of the nascent 69342 Lyon, France
cycle. For 9, the water molecule is outside the forming ring but Daniel L. Nascimento − Center for Catalysis Research &
nevertheless stabilizes the linear conformation. Indeed, water Innovation, and Department of Chemistry and Biomolecular
destabilizes the precyclic conformation even more strongly for Sciences, University of Ottawa, Ottawa, Ontario K1N 6N57,
9 than for 1 (by 5.6 or 2.7 kcal/mol, respectively: Figure 4b),44 Canada; orcid.org/0000-0002-9363-2175
in part by disrupting the CC π-stacking arrangement seen Alexandre Y. Goudreault − Center for Catalysis Research &
for anhydrous 9. Innovation, and Department of Chemistry and Biomolecular
Sciences, University of Ottawa, Ottawa, Ontario K1N 6N57,
The unexpectedly greater negative impact of H2O on
Canada; orcid.org/0000-0002-4075-9228
cyclization of 9 is supported by experiment. On repeating the
Stephan N. Steinmann − Univ. Lyon, ENS de Lyon, CNRS
RCM of 9 at the 5 mM diene concentration employed in
UMR 5182, Université Claude Bernard Lyon 1, Laboratorie
mRCM, using the most robust catalyst Ru-3, we observe lower
de Chimie, F-69342 Lyon, France; orcid.org/0000-0002-
catalyst water-tolerance for 9 than 1 (30% vs 73%; Figure S3).
2777-356X
Water thus has a greater negative impact on 9 than 1. By
retarding the rate of metathesis relative to catalyst decom- Complete contact information is available at:
position, H-bonded water can exacerbate catalyst decom- https://pubs.acs.org/10.1021/acscatal.0c04279
position, further limiting RCM performance in the presence of
water. Notes
The authors declare no competing financial interest.
■
The foregoing demonstrates that even low levels of water
severely degrade the productivity of leading ruthenium
catalysts in olefin metathesis. This is an important clue to ACKNOWLEDGMENTS
the pathways by which water triggers decomposition: it points This work was funded by the Natural Sciences and Engineering
toward direct attack by water on the catalyst, independent of Research Council of Canada (NSERC), the Research Council
any effects arising from water as a medium. Fast-initiating of Norway (RCN, project 288135), and Centre National de la
catalysts prove particularly vulnerable. Maximum productivity Recherche Scientifique: SYSPROD and AXELERA Pôle de
is seen for slower-initiating, bulkier iodide and CAAC catalysts, Compétitivité (PSMN Data Center). The University of
which emerge as the systems of choice where drying is Ottawa, CNRS, and ENS Lyon are thanked for support via
impractical, or where water is an essential cosolvent. These the International Associated Laboratory ‘Fundamental Catal-
findings represent the first insights into structure−decom- ysis for Green Chemistry’ (FUNCAT). Apeiron is thanked for
gifts of CAAC catalysts.
■
position relationships for olefin metathesis in the presence of
water. They are expected to aid in deconvoluting the
mechanisms by which water causes decomposition and DEDICATION
ultimately design of truly water-tolerant olefin metathesis Dedicated to P. H. Dixneuf, in honor of his outstanding
catalysts. contributions to organometallic chemistry and catalysis.
896 https://dx.doi.org/10.1021/acscatal.0c04279
ACS Catal. 2021, 11, 893−899
ACS Catalysis
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pubs.acs.org/acscatalysis Letter
897 https://dx.doi.org/10.1021/acscatal.0c04279
ACS Catal. 2021, 11, 893−899
ACS Catalysis pubs.acs.org/acscatalysis Letter
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Figure 3.
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