10.1002/cctc.201902258
ChemCatChem
COMMUNICATION
Scheme 3. Synthesis and the stereoisomers of 9 - 11 Ru-CAAC complexes.
Acknowledgements
OH
EtO2C CO2Et
Thanks are due for the support provided by the European Union
and the State of Hungary, co-financed by the European
Regional Development Fund in the framework of the project No.
VEKOP-2.3.2-16-2017-00013. This work was funded by grants
provided by the National Competitiveness and Excellence
Program, Hungary (NVKP-16-1-2016-0007). P. Bombicz thanks
the National Research, Development and Innovation Office-
NKFIH for OTKA K115762 and K124544 grants. The authors
thank Prof. Sándor Kéki (University of Debrecen) for HRMS
analysis, Dr. Szabolcs Balogh, Dr. Gergely Farkas (both at
University of Pannonia) and Dr. Tibor Nagy (TTK AKI) for useful
discussions.
OH
EtO2C CO2Et
n
n
17
OH
18
14
13
OH
OH
OH
HO
18
HO
15
19
16
O
O
R
+
R
MeO
MeO
7
7
7
7
+
20
21
22
R
R
24
O
O
R
O
O
O
O
O
O
7
7
7
7
Keywords: Olefin metathesis, CAAC ligand, protic media,
O
O
R
+
ruthenium, sustainable catalysis
2 R
7
7
7
+
22
R
R
O
P
O
P
24
N
N
O
O
[1]
I. Chorkendorff, J. W. Niemantsverdriet, Eds. , in Concepts Mod. Catal.
Kinet., Wiley-VCH Verlag GmbH & Co. KGaA, 2012, pp. 1–22.
A. H. Hoveyda, A. R. Zhugralin, Nature 2007, 450, 243–251.
J. C. Mol, J. Mol. Catal. A Chem. 2004, 213, 39–45.
R. H. Grubbs, Ed. , Handbook of Metathesis, Wiley-VCH, Weinheim,
2013.
O
O
[2]
[3]
[4]
23
22, 24, 25: R = CH2OAc
25
Table 1. Results of olefin metathesis reactions
T
t
(h)
3
Y
(%)
29
Entry
Solv.
M
S
P
C
Mol%
TON
( C)
°
RT
[5]
[6]
D. R. Anderson, V. Lavallo, D. J. O’Leary, G. Bertrand, R. H. Grubbs,
Angew. Chemie - Int. Ed. 2007, 46, 7262–7265.
1
13
14
10
0.05
580
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
M
M
IPA
M
M
M
M/W
neat
W
neat
M
M
M
neat
M
M
13
15
15
15
17
17
17
17
17
17
19
19
20
20
20
23
23
23
14
16
16
16
18
18
18
18
18
18
18
18
22
22
22
22
22
22
12
10
10
12
10
10
10
11
10
12
10
12
10
11
12
10
11
12
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
<0.50
0.05
0.50
0.50
0.05
0.05
0.05
0.50
4.2
65
RT
RT
65
RT
RT
RT
65
RT
65
RT
65
RT
65
65
RT
65
3
3
3
3
3
24
24
3
24
3
3
3
24
3
3
24
3
64
36
56
30
65
79
32
33
99
50
39
50
NR
99
41
57
NR
80
1280
780
P. Wyrebek, P. Maecki, A. Sytniczuk, W. Kośnik, A. Gawin, J.
Kostrzewa, A. Kajetanowicz, K. Grela, ACS Omega 2018, 3, 18481–
18488.
1120
a
-
1300
1580
640
660
>200
1000
78b
[7]
[8]
[9]
I. Rozenberg, O. Eivgi, A. Frenklah, D. Butilkov, S. Kozuch, I. Goldberg,
N. G. Lemcoff, ACS Catal. 2018, 8, 8182–8191.
D. Butilkov, A. Frenklah, I. Rozenberg, S. Kozuch, N. G. Lemcoff, ACS
Catal. 2017, 7, 7634–7637.
D. R. Anderson, T. Ung, G. Mkrtumyan, G. Bertrand, R. H. Grubbs, Y.
Schrodi, Organometallics 2008, 27, 563–566.
100b
NR
1980
820
114
NR
[10] J. Tomasek, J. Schatz, Green Chem. 2013, 15, 2317–2338.
[11] A. Jana, K. Grela, Chem. Commun. 2018, 54, 122-139.
[12] M. Smoleń, A. Marczyk, W. Kośnik, B. Trzaskowski, A. Kajetanowicz, K.
Grela, European J. Org. Chem. 2019, 640–646.
M
M
4.2
65
3
19
[13] A. A. Rajkiewicz, K. Skowerski, B. Trzaskowski, A. Kajetanowicz, K.
Grela, ACS Omega 2019, 4, 1831–1837.
[a] mass formed; [b] mixture of 17 and 18; Solvents: (M) methanol, (IPA)
isopropyl alcohol, (W) water. (Y): reaction yield, NR: no reaction.
[14] J. Czaban, C. Torborg, K. Grela, in Sustain. Catal. Challenges Pract.
Pharm. Fine Chem. Ind. (Eds.: P. J. Dunn, K. K.(Mimi), Hii, M. J.
Krische, M. T. Williams), Wiley, 2013, pp. 163–214.
The cross-metathesis of DOPC (23) as model compound with
0.5 mol% loading of catalyst 10 gave a reasonable yield (57%)
to the target compound (22) in methanol. Interestingly, catalyst
11 was inactive for the reaction. However, 12 was also very
effective with 80 % yield, although at a high catalyst loading of
4.2 mol%.
[15] A. Michrowska, Ł. Gułajski, Z. Kaczmarska, K. Mennecke, A. Kirschning,
K. Grela, Green Chem. 2006, 8, 685–688.
[16] B. Mohr, D. M. Lynn, R. H. Grubbs, Organometallics 1996, 15, 4317–
4325.
[17] T. A. Kirkland, D. M. Lynn, R. H. Grubbs, J. Org. Chem. 1998, 63,
9904–9909.
In summary, new ruthenium-CAAC olefin metathesis catalysts
have been synthetized, which are soluble in protic solvents
showing exceptional stability and catalytic activity. It has been
demonstrated that catalytic reactions of OH functionalized
feedstock (RCM, ROMP, CM and isomerization) can be carried
out at as low as 0.05 mol % catalyst loading in methanol,
isopropanol, water or methanol/water solvent mixture. It has also
been shown that the cross-metathesis of renewable feedstocks,
such as methyl linoleate can be carried out in environmental
benign protic media at low catalyst loading. Further research is
underway to determine the exact structures in solutions and the
[18] D. M. Lynn, B. Mohr, R. H. Grubbs, L. M. Henling, M. W. Day, J. Am.
Chem. Soc. 2000, 122, 6601–6609.
[19] J. P. Gallivan, J. P. Jordan, R. H. Grubbs, Tetrahedron Lett. 2005, 46,
2577–2580.
[20] S. H. Hong, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 3508–3509.
[21] V. M. Marx, A. H. Sullivan, M. Melaimi, S. C. Virgil, B. K. Keitz, D. S.
Weinberger, G. Bertrand, R. H. Grubbs, Angew. Chemie - Int. Ed. 2015,
54, 1919–1923.
[22] J. Zhang, S. Song, X. Wang, J. Jiao, M. Shi, Chem. Commun. 2013, 49,
9491–9493.
[23] R. Gawin, A. Kozakiewicz, P. A. Guńka, P. Dąbrowski, K. Skowerski,
Angew. Chemie - Int. Ed. 2017, 56, 981–986.
thermodynamic
diastereomers.
parameters
of
the
rotamers
and/or
[24] D. L. Nascimento, A. Gawin, R. Gawin, P. A. Guńka, J. Zachara, K.
Skowerski, D. E. Fogg, J. Am. Chem. Soc. 2019, 141, 10626–10631.
4
This article is protected by copyright. All rights reserved.