Synthesis and reactivity of oxygen chelated ruthenium carbene metathesis catalysts

Article abstract of DOI:10.1016/j.jorganchem.2014.01.017

The rate of initiation of Hoveyda catalysts is affected by the electronic and steric effects that act upon the Rua?O coordination. In order to boost the activity of Hoveyda catalysts, a series of new oxygen chelated ruthenium carbene metathesis catalysts containing an N-heterocyclic carbene (NHC) and a carbonyl group has been developed, and their catalytic activities for olefin metathesis reactions were investigated. The aliphatic end groups of complexes (H₂IMes)(Cl)₂RuC(H)[(C₆H ₃X)OCH(Me)(C(O)OEt)(X = H, OMe, Me, NO₂)] were functionalized by the attachment of a straight-chain ester. The X-ray structures of complex (H₂IMes)(Cl)₂RuC(H)[(C₆H ₄)OCH(Me)(C(O)NMe₂)] showed that the carbonyl oxygen of the amide and the terminal oxygen of the benzylidene ether are both coordinated to the metal to give an octahedral structure. However, the carbonyl oxygen of complexes (H₂IMes)(Cl)₂RuC(H)[(C₆H ₃X)OCH(CH₂C(O)OCH₂)(X = H, OMe)] does not coordinate to the metal due to the steric effect of the lactone. All these complexes were used as catalysts for olefin metathesis reactions and all exhibited excellent performances for the ring-closing metathesis (RCM) of diethyl diallymalonate at 30 C. The initiation rate of these catalysts was higher than that for the Hoveyda catalyst ((H₂IMes)(Cl) ₂RuC(H)(C₆H₄-2-OⁱPr)) and these complexes are also active for cross metathesis (CM).

Full text of DOI:10.1016/j.jorganchem.2014.01.017

Journal of Organometallic Chemistry 756 (2014) 1e9
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and reactivity of oxygen chelated ruthenium carbene
metathesis catalysts
Yiran Zhang a, Mingbo Shao b, Huizhu Zhang a, Yuqing Li a, Dongyu Liu a, Yu Cheng a,
,
b,
**
Guiyan Liu a , Jianhui Wang
*
a College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of InorganiceOrganic Hybrid
Functional Material Chemistry (Tianjin Normal University), Ministry of Education, Tianjin Normal University, Tianjin 300387, PR China
b Department of Chemistry, College of Science, Tianjin University, Tianjin 300072, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The rate of initiation of Hoveyda catalysts is affected by the electronic and steric effects that act upon the
Ru/O coordination. In order to boost the activity of Hoveyda catalysts, a series of new oxygen chelated
ruthenium carbene metathesis catalysts containing an N-heterocyclic carbene (NHC) and a carbonyl
group has been developed, and their catalytic activities for olefin metathesis reactions were investigated.
The aliphatic end groups of complexes (H2IMes)(Cl)2Ru]C(H)[(C6H3X)OCH(Me)(C(O)OEt)(X ¼ H, OMe,
Me, NO2)] were functionalized by the attachment of a straight-chain ester. The X-ray structures of
complex (H2IMes)(Cl)2Ru]C(H)[(C6H4)OCH(Me)(C(O)NMe2)] showed that the carbonyl oxygen of the
amide and the terminal oxygen of the benzylidene ether are both coordinated to the metal to give an
octahedral structure. However, the carbonyl oxygen of complexes (H2IMes)(Cl)2Ru]C(H)[(C6H3X)
OCH(CH2C(O)OCH2)(X ¼ H, OMe)] does not coordinate to the metal due to the steric effect of the lactone.
All these complexes were used as catalysts for olefin metathesis reactions and all exhibited excellent
performances for the ring-closing metathesis (RCM) of diethyl diallymalonate at 30 ꢀC. The initiation rate
of these catalysts was higher than that for the Hoveyda catalyst ((H2IMes)(Cl)2Ru]C(H)(C6H4-2-OiPr))
and these complexes are also active for cross metathesis (CM).
Received 12 November 2013
Received in revised form
8 January 2014
Accepted 17 January 2014
Keywords:
Olefin metathesis
Ruthenium
N-Heterocyclic carbenes
Homogeneous catalysis
Ó 2014 Elsevier B.V. All rights reserved.
1. Introduction
ruthenium catalyst lead to greatly increased initiation rates for
different metathesis reactions even at 0 ꢀC. Around the same time,
Since the discovery of well-defined modern ruthenium catalysts
1e4 (Chart 1) [1], olefin metathesis as one of the most important
tools for constructing carbonecarbon double bonds has been
widely used in organic synthesis, materials science, and biochem-
istry [2]. Among these complexes, Grubbs second-generation
ruthenium carbene catalyst 2 possesses a high activity and an
excellent tolerance for a variety of functional groups. Ruthenium-
benzylidene catalyst 4 which bears N-heterocyclic carbene (NHC)
ligand, exhibits extraordinary activity and stability was introduced
by Hoveyda and coworker [1c]. It is widely used in reuse and
immobilization of the catalyst [3e5]. However, a large isopropoxy
Grela et al. developed complex 6 which has an electron-
withdrawing substituent (a nitro group) [7]. Under very mild
conditions (even at 0 ꢀC) it was successfully applied to various types
of olefin metathesis (ring-closing metathesis, cross metathesis and
enyne metathesis). Both complexes 5 and 6 destabilize the oxygen/
metal interaction which favors faster access to the formation of the
14-electron Ru carbene species; these results in increasing catalytic
activity [8].
However, as mentioned by Conrad et al. [9], the global efficiency
of an olefin metathesis catalyst not only has a high initiation rate
and a high selectivity, but also has extraordinary stability and the
stability of the precatalyst plays an important role. In order to boost
the stability of the catalyst, many improvements have been made
including changing the N-heterocyclic carbine [10] and the leaving
group [11]. So, many highly efficient and stable Ru carbene
metathesis catalysts have been designed based on complex 4
[12,13].
i
group and the donation of an electron from PrO to ruthenium
cause this catalyst to initiate more slowly than Grubbs catalyst 2.
In 2002, Wakamatsu and Blechert synthesized complex 5 by
modifying the neighboring bulky phenyl group [6]. This phenyl
Complex 7a and 7b were developed by Bieniek et al., in 2006
[12b]. The aliphatic end groups of the complexes were functional-
ized by attaching an ester group which enhanced the leaving group
* Corresponding author. Fax: þ86 022 23766532.
** Corresponding author. Fax: þ86 22 27403475.
E-mail addresses: guiyanliu2013@163.com (G. Liu), wjh@tju.edu.cn (J. Wang).
0022-328X/$ e see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2014.01.017

2
Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
Chart 1. Ruthenium metathesis catalysts.
properties of the styrenyl ether. X-ray results showed that the
carbonyl oxygen of the ester group in these complexes coordinated
to the metal. Furthermore, complex 7b which has an electron
withdrawing NO2 group gave high turnover numbers.
The rate of initiation of chelated complexes is affected by the
electronic and steric effects that act upon the Ru/O coordination.
In 2011, Bieniek et al. synthesized a series of complexes 8e11 with
different substituents (an ester group, a ketonic group, or a malonic
Chart 2. New oxygen chelated ruthenium carbene metathesis catalysts.

Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
3
Scheme 1. Synthesis of ruthenium carbonyl 17 complexes.
Scheme 2. Synthesis of ruthenium carbonyl 18a and 18b complexes.
Scheme 3. Synthesis of ruthenium carbonyl 19a and 19b complexes.
group). All of these complexes had an additional functional group
the coordinated to the metal center [12c]. All these catalysts were
found to exhibit higher activities than that of the unmodified
complex 4 in ring-closing metathesis (RCM) and cross metathesis
(CM) reactions for both standard and challenging substrates.
Recently, Wu et al. replaced the phenyl group with an electron-
deficient pyrimidine unit and prepared a new type of N-heterocy-
clic carbene catalyst 12 [13]. The presence of an electron-deficient
pyrimidine structure greatly enhanced the catalytic activities of
the new NHC ruthenium complex. In addition, other methods have
been used, including the changes of NHC-systems [14].
On the basis of these previous research; a series of new NHC
ruthenium complexes 17, 18 and 19 (Chart 2) in which the leaving
group properties of the styrenyl ether were enhanced by attaching
an ester or amide functional group to the aliphatic end group is
reported herein.
2. Results and discussion
The synthesis of some new ethoxycarbonyl substituted com-
plexes is depicted in Scheme 1. Ester-substituted styrenyl ethers
were prepared as carbene ligand precursors by reacting commer-
cially available 13aed with 2-bromo-propionic acid ethyl ester in
the presence of potassium carbonate. The precursors (14aed) were
then reacted with a Grubbs second-generation catalyst in the
presence of copper (I) chloride in CH2Cl2 at 40 ꢀC, as described by
Kingsbury et al. [1c]. This resulted in the exchange of the styrene
Table 1
Selected bond angles (deg).
Cl(1)eRu(1)e C(1)eRu(1)e C(28)eRu(1)e C(1)eRu(1)e O(1)eRu(1)e
Cl(2)
O(1)
O(1)
Cl(2)
Cl(1)
18a 168.159(106) 172.234(332) 80.581(383)
19a 159.590(35) 177.635(118) 78.916(144)
19b 154.391(104) 178.518(336) 80.509(335)
96.104(304) 82.867(199)
92.988(99) 85.693(68)
97.293(297) 84.675(205)
Fig. 1. Perspective view of the catalyst 18a. Ellipsoids are drawn at the 50% probability
level.

4
Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
Table 2
ꢀ
Selected interatomic distances (A).
Ru(1)e
Ru(1)e
Ru(1)e
Ru(1)e
Ru(1)e
Ru(1)e
C(28)
C(1)
Cl(1)
Cl(2)
O(1)
O(2)
18a
19a
19b
1.820
1.828
1.806
1.978
1.974
2.037
2.363
2.364
2.315
2.385
2.345
2.265
2.186
2.242
2.341
2.348
group to give the desired catalysts in good yield (17a-62.6%, 17b-
64.2%, 17c-62.6%, and 17d-67.7%) as greenish crystalline solids.
The synthesis of amide substituted complexes 18a and 18b is
shown in Scheme 2. The N,N-dimethyl substituted carbene ligand
amide precursors (15a,b) were obtained by hydrolysis and acyl-
ation of 14a,b. An exchange reaction between 15a,b and a Grubbs
second-generation catalyst in the presence of copper(I) chloride
afforded the desired catalysts 18a and 18b, in good yields (66.8%,
to 65.2% respectively) in the form of green crystalline
compounds.
Scheme
3 illustrates the synthesis of new ring lactone
substituted Grubbs/Hoveyda second-generation catalysts. Ring
lactone substituted styrenyl ethers 16a and 16b were prepared as
carbene ligand precursors by the reaction of commercially available
13a and 13b with 3-bromo-dihydrofuran-2-one in the presence of
potassium carbonate. These precursors were then reacted with a
Grubbs second-generation catalyst in the presence of copper(I)
chloride in CH2Cl2 at 40 ꢀC, to give the desired catalysts 19a and 19b
in good yields (64.0% and 64.2%) as greenish crystalline solids.
Crystals of the new Ru complex 18a was grown by slow evap-
oration from CH2Cl2/ethyl acetate. The molecular structures of the
two complexes are shown in Fig. 1. Some of the interatomic dis-
tances and bond angles are given in Tables 1 and 2. The X-ray
structures show that the arrangements of the ligands around the
metal centers have characteristics in common with those found in
the Grubbs/Hoveyda second-generation complex. However, 18a
additionally has a weak bonding interaction between the carbonyl
oxygen of the ester group and the ruthenium center. This enhances
their stability in air and makes them easier to purify with silica gel
column chromatography. The interatomic distances (Ru(1)e
Fig. 3. Catalytic activities of 17, 18, 19 and 4 in the RCM of diallyl diethylmalonate
(CH2Cl2, 1 mol % ruthenium precatalyst), 30 ꢀC, 30 min, conversions calculated from 1H
NMR results.
conversion rates for RCM by 17, 18 and 19 under similar conditions
are shown in Figs. 3e5. At 30 ꢀC, except the polyfunctional “nitro-
ester” catalyst 17d exhibiting excellent performance, the catalytic
activities of 17, 18 and 19 are slightly higher than that of the un-
modified 4 using diallylmalonate (Fig. 3) as substrate. All the cat-
alysts, high RCM conversions of 20 (>97%) were achieved after
30 min at 30 ꢀC. In order to clearly compare the efficiencies of the
above complexes, they were used in RCM reactions at 0 ꢀC with
diallylmalonate (Fig. 4) or diallyltosylamide (Fig. 5) as the substrate.
All the ligand modifications resulted in an enhancement in the
activity relative to those of the unmodified 4. The ester catalysts
17aec and the amide catalysts 18a,b have weak bonding in-
teractions between the carbonyl oxygen and the ruthenium center
and they all exhibit very good performance with similar conver-
sions after 6 h. The catalytic activities of the ester catalysts 17aec
are similar to complex 7a and are lower than complex 10. It is
noteworthy that the polyfunctional “nitro-ester” catalyst 17d
exhibited excellent performance for both substrates and is similar
to complex 7b [12c]. Also of note, is that catalysts 19a and 19b,
whose carbonyl oxygen ligands do not interact with the metal,
ꢀ
O(2) ¼ 2.348 A for 18a) between the carbonyl groups and the metal
Ru centers are shorter than those for complexes (7e11) containing
ester groups.
Complexes 19a and 19b are different from 18a in that the
carbonyl oxygen does not coordinated with the metal center due to
the effect of the five membered lactone ring. In 19a and 19b, only
the ether oxygen coordinated with the Ru. The X-ray structures are
shown in Fig. 2.
The catalytic activity of 17, 18 and 19 for RCM was tested with
diethyl diallylmalonate 20 and diallyltosylamide 22. The relative
Fig. 2. Perspective view of the catalyst 19a (left) and 19b (right). Ellipsoids are drawn at the 50% probability level.

Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
5
substrate 34 (see Table 3). These reactions resulted in the formation
of either five-, six- or seven-membered rings with di- or trisub-
stituted double bonds. The products were obtained in high con-
versions at 35 ꢀC with low catalyst loading (0.05e0.5 mol%). For the
bulky-substituted dienes 36, complexes 17, 18, 19 all gave low
conversions at 35 ꢀC in CH2Cl2. However RCM was achieved in good
conversions for all catalysts at elevated temperatures (80 ꢀC in
toluene) with high catalyst loading (1.0e2.0 mol%) and a longer
reaction time (24 h). Cross metathesis of olefins 42 and 43 also
produced high yields of new alkene product 44 when 0.05e1.0 mol
% of catalyst was used (Table 3, entry 12). Thus, 17, 18 and 19 are
highly active catalysts for a wide range of RCM reactions. They are
active with many functional groups which is similar to the behavior
of the parent complex 4.
3. Conclusions
In order to boost the rate of initiation and the stability of Hov-
eyda catalysts, a series of new oxygen chelated ruthenium carbene
metathesis catalysts containing carbonyl groups were presented.
These catalysts have an extra coordinating group (an ester or
amide) which gives additional protection to the metal center.
Interestingly, all these catalysts were found to exhibit higher ac-
tivity and stability than the unmodified Hoveyda prototype 4 in
RCM and CM reactions for wide range substrates. This work pro-
vides a good theoretical basis for the design of new types of olefin
metathesis catalysts.
Fig. 4. Catalytic activities of 17, 18, 19 and 4 in the RCM of diallyl diethylmalonate
(CH2Cl2, 1 mol % ruthenium precatalyst), 0 ꢀC, 6 h, conversions calculated from 1H NMR
results.
4. Experiment
initiated more rapidly than the others catalysts (except 17d). So, 17,
18 and 19 are all highly active RCM catalysts.
Further studies showed that 17, 18 and 19 are also active for ring
closures of substrates with N-protected substrates 22, 24, 28, 30, 32,
4.1. General procedure for preparation of 14aed
A flask was charged with dry acetone (8 mL), K2CO3 (0.5 g,
3.7 mmol) and 13aed (2.5 mmol). The mixture was heated to 50 ꢀC
and alpha bromo ethyl propionate (0.6 g, 3.3 mmol) was slowly
added. Then, the reaction mixtures were stirred for 3 h under
reflux. After cooling to room temperature, the mixtures were
filtered and concentrated to afford the crude product. The crude
product was purified by silica gel chromatography (pentanes:
CH2Cl2 ¼ 1:1).
oxygen-containing substrates 38, 40, and
a sulfur-containing
4.1.1. Ethyl-2-(2-(prop-1-enyl)phenoxy)propanoate (14a)
Colorless oil. Yield: 95.0%. Analytical Data. Calcd (found) for
C14H18O3: C, 71.77 (71.56); H, 7.74 (7.78). 1H NMR (400 MHz, CDCl3)
d
(ppm): 1.25 (t, J ¼ 6.9 Hz, 3H), 1.63 (d, J ¼ 6.3 Hz, 3H), 1.90 (d,
J ¼ 6.7 Hz, 3H), 2.57 (d, J ¼ 6.5 Hz, 3H), 4.19 (dd, J ¼ 13.6 Hz, 6.3 Hz,
2H), 4.70 (dd, J ¼ 13.8 Hz, 6.1 Hz,1H), 6.18 (m,1H), 6.70 (m, 2H), 6.87
(m, 1H), 7.04 (m, 1H), 7.38 (d, J ¼ 7.4 Hz, 1H). 13C NMR (100 MHz,
CDCl3) d: 14.3, 18.8, 19.2, 61.4, 73.6, 113.3, 121.9, 125.7, 126.6, 126.8,
127.7, 130.6, 154.6, 172.4 ppm. IR (KBr)
n: 3065, 2984, 2932, 2852,
1762, 1606, 1486, 1369, 1253, 1217, 1054, 964, 836, 769 cmꢁ1
.
4.1.2. Ethyl-2-(4-methoxy-2-(prop-1-enyl)phenoxy)propanoate
(14b)
Colorless oil. Yield: 94.2%. Analytical Data. Calcd (found) for
C
15H20O4: C, 68.16 (68.19); H, 7.63 (7.70). 1H NMR (400 MHz, CDCl3)
d
(ppm): 1.25 (t, J ¼ 6.8 Hz, 3H), 1.61 (d, J ¼ 6.7 Hz, 3H), 1.91 (q,
J ¼ 6.6 Hz, 3H), 3.76 (s, 3H), 4.21 (q, J ¼ 6.7 Hz, 2H), 4.62 (q,
J ¼ 7.2 Hz, 1H), 6.18 (m, 1H), 6.64 (m, 3H), 6.96 (d, J ¼ 2.8 Hz, 1H). 13
C
NMR (100 MHz, CDCl3) d: 14.3, 18.8, 19.1, 55.8, 61.3, 74.8, 111.7, 112.8,
115.7, 125.7, 127.1, 129.5, 148.9, 154.7, 172.6 ppm. IR (KBr)
2986, 2938, 2835, 1751, 1653, 1607, 1584, 1492, 1393, 1376, 1278,
1211, 1096, 1046, 970, 948, 857, 811, 732 cmꢁ1
n: 3083,
Fig. 5. Catalytic activity of 17, 18, 19 and 4 in the RCM of N-protected substrate 22
(CH2Cl2, 1 mol % ruthenium precatalyst), 0 ꢀC, 6 h, conversions calculated from 1H NMR
results.
.

6
Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
Table 3 (continued)
Table 3
Application of catalysts 17, 18 and 19 to different substrates.
Entry
Diene
Product
Cat. (mol %) Conditionsa Yield (%)c
Entry
Diene
Product
Cat. (mol %) Conditionsa Yield (%)c
17d (0.05) 0.5 h
98
98
97
98
98
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h
0.5 h
0.5 h
0.5 h
1
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
98
97
99
98
97
98
98
17d (0.05) 0.5 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h
0.5 h
0.5 h
0.5 h
9
17a (2.0)
17b (2.0)
17c (2.0)
17d (1.0)
18a (2.0)
18b (2.0)
19a (2.0)
19b (2.0)
24.0 hb
24.0 hb
24.0 hb
24.0 hb
24.0 hb
24.0 hb
24.0 hb
24.0 hb
95
94
93
95
95
94
95
94
2
3
4
5
6
7
8
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
98
97
99
98
97
99
98
17d (0.05) 0.5 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h
0.5 h
0.5 h
0.5 h
10
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
96
96
98
98
94
98
97
17d (0.05) 0.5 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h,
0.5 h
0.5 h
0.5 h
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
98
97
98
98
98
98
98
17d (0.05) 0.5 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h,
0.5 h
0.5 h
0.5 h
11
17a (0.5)
17b (0.5)
17c (0.5)
12.0 h
12.0 h
12.0 h
97
95
95
97
94
94
96
96
17d (0.05) 12.0 h
18a (0.5)
18b (0.5)
19a (0.5)
19b (0.5)
12.0 h
12.0 h
12.0 h
12.0 h
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
98
98
99
98
98
98
98
17d (0.05) 0.5 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h
0.5 h
0.5 h
0.5 h
12
17a (1.0)
17b (1.0)
17c (1.0)
24.0 h
24.0 h
24.0 h
94
94
93
94
93
92
94
93
17d (0.05) 24.0 h
18a (1.0)
18b (1.0)
19a (1.0)
19b (1.0)
24.0 h
24.0 h
24.0 h
24.0 h
17a (0.1)
17b (0.1)
17c (0.1)
0.3 h
0.3 h
0.3 h
99
99
98
98
98
98
99
99
a
Reactions were conducted at 35 ꢀC in CH2Cl2.
In toluene at 80 ꢀC.
17d (0.05) 0.3 h
b
c
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.3 h
0.3 h
0.3 h
0.3 h
Isolated yields after silica gel chromatography. Yields determined by 1H NMR
spectroscopy.
4.1.3. Ethyl-2-(4-nitro-2-(prop-1-enyl)phenoxy)propanoate (14c)
17a (0.1)
17b (0.1)
17c (0.1)
1.0 h
1.0 h
1.0 h
98
98
98
98
98
98
98
98
Colorless oil. Yield: 92.6%. Analytical Data. Calcd (found) for
C
14H17NO5: C, 60.21 (60.19); H, 6.14 (6.17); N, 5.02 (5.05). 1H NMR
(400 MHz, CDCl3)
d
(ppm): 1.25 (t, J ¼ 7.1 Hz, 3H), 1.71 (d, J ¼ 6.7 Hz,
17d (0.05) 1.0 h
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
1.0 h
1.0 h
1.0 h
1.0 h
3H), 1.95 (q, J ¼ 6.5 Hz, 3H), 4.22 (q, J ¼ 7.1 Hz, 2H), 4.85 (q,
J ¼ 6.7 Hz,1H), 6.37 (m, 1H), 6.74 (m, 2H), 8.02 (d, J ¼ 9.0 Hz,1H), 8.3
(s, 1H). 13C NMR (100 MHz, CDCl3)
d: 14.3, 18.6, 19.1, 61.9, 73.5,
111.914, 122.3, 123.5, 123.9, 128.7, 129.9, 142.2, 158.9, 171.1 ppm. IR
(KBr) : 3076, 2987, 2940, 2869, 1750, 1653, 1609, 1584, 1516, 1485,
1344, 1255, 1201, 1095, 1049, 967, 816, 746, 657 cmꢁ1
n
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
98
97
98
98
97
98
98
.
17d (0.05) 0.5 h
4.1.4. Ethyl-2-(4-methyl-2-(prop-1-enyl)phenoxy)propanoate
(14d)
18a (0.1)
18b (0.1)
19a (0.1)
19b (0.1)
0.5 h
0.5 h
0.5 h
0.5 h
Colorless oil. Yield: 97.7%. Analytical Data. Calcd (found) for
C
d
15H20O3: C, 72.55 (72.51); H, 8.12 (8.15). 1H NMR (400 MHz, CDCl3)
(ppm): 1.27 (t, J ¼ 6.3 Hz, 3H), 1.64 (d, J ¼ 6.5 Hz, 3H), 1.93 (q,
J ¼ 6.6 Hz, 3H), 2.29 (s, 3H), 4.22 (q, J ¼ 6.7 Hz, 2H), 4.72 (q,
J ¼ 6.3 Hz, 1H), 5.99 (m, 1H), 6.62 (m, 2H), 6.93 (m, 1H), 7.24 (d,
17a (0.1)
17b (0.1)
17c (0.1)
0.5 h
0.5 h
0.5 h
98
97
97
J ¼ 6.7 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d: 14.1, 18.6, 18.9, 34.4,
61.1, 73.1, 112.1, 115.3, 126.2, 127.1, 127.4, 128.0, 130.8, 137.2, 153.3,

Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
7
172.4 ppm. IR (KBr)
n
: 3081, 2983, 2936, 2869, 1755, 1637, 1499,
4.3.1. 3-(2-(Prop-1-enyl)phenoxy)-dihydrofuran-2-one (16a)
1375, 1272, 1243, 1137, 1096, 1052, 870, 903, 805 cmꢁ1
.
Light yellow oil. Yield: 90.0%. Analytical Data. Calcd (found) for
13H14O3: C, 71.54 (71.48); H, 6.47 (6.42). 1H NMR (400 MHz, CDCl3)
(ppm): 1.65 (d, J ¼ 6.5 Hz, 3H), 1.94 (q, J ¼ 6.6 Hz, 3H), 2.29 (s, 3H),
C
d
4.2. General procedure for preparation of 15aed
2.95 (s, 3H), 3.09 (s, 3H), 4.90 (q, J ¼ 6.2 Hz, 1H), 6.01 (m, 1H), 6.65
(m, 2H), 6.95e6.99 (m, 1H), 7.28 (d, J ¼ 6.8 Hz, 1H). 13C NMR
A flask was charged with 14aed (2.1 mmol) and NaOH (6.2 mL,
10.0%). The reaction mixtures were stirred for 5 h under reflux.
After cooling to 0 ꢀC, HCl (6 M) was added until the pH was 3e4.
Stirring was continued for 15 min at 0 ꢀC. The precipitate was then
filtered and washed with water. After drying the desired acids were
obtained. Under N2, the acid (1.2 mmol) was charged with SOCl2 at
50 mL Schlenk. After the reaction, the mixture was stirred for 2 h
under reflux, and then the SOCl2 was removed. Next 2 mL of dry
benzene and dimethylamine (40%, 2.0 eq) were added at 0 ꢀC under
N2. The reaction mixture was stirred at room temperature for 12 h.
The organic layer was removed and the aqueous layer was extrac-
ted with benzene. The organic layers were combined and washed
with saturated salt water, dried over magnesium sulfate, filtered
and concentrated. Purification by flash column chromatography on
silica (CH2Cl2) gave the desired product.
(100 MHz, CDCl3) d: 19.1, 30.1, 65.6, 73.5, 114.8, 122.8, 125.3, 126.8,
127.4, 128.0, 130.7, 154.1, 173.8 ppm. IR (KBr)
2908, 2874, 1785, 1592, 1485, 1450, 1375, 1239, 1220, 1120, 1018,
993, 948, 753 cmꢁ1
n: 3031, 2997, 2964,
.
4.3.2. 3-(4-Methoxy-2-(prop-1-enyl)phenoxy)-dihydrofuran-2-one
(16b)
Colorless oil. Yield: 88.2%. Analytical Data. Calcd (found) for
C
13H14O3: C, 71.54 (71.51); H, 6.47 (6.50). 1H NMR (400 MHz, CDCl3)
d
(ppm): 1.89 (d, J ¼ 5.0 Hz, 3H), 2.68 (m, 1H), 2.75 (m, 1H), 4.39 (m,
1H), 4.45 (m, 1H), 4.91 (q, J ¼ 7.8, 1H), 6.21 (m, 1H), 6.70 (d, J ¼ 10.1,
1H), 6.98 (m, 2H), 7.16 (m, 1H), 7.43 (d, J ¼ 7.7, 1H). 13C NMR
(100 MHz, CDCl3) d: 19.1, 30.1, 55.8, 65.5, 74.8, 11.7, 113.144, 117.57,
125.249, 127.8, 129.8, 148.6, 155.4, 173.9 ppm. IR (KBr)
2914, 2836, 1791, 1603, 1583, 1506, 1378, 1290, 1217, 1167, 1097,
1035, 888, 811, 757, 739, 696, 661 cmꢁ1
n: 3037, 2999,
.
4.2.1. 2-(2-(Prop-1-enyl)phenoxy)propanoic acid (15a)
4.4. General synthesis of the catalysts
Yellow oil. Yield: 65.1%. Analytical Data. Calcd (found) for
C
14H19NO2: C, 72.07 (72.12); H, 8.21 (8.17); N, 6.00 (6.09). 1H NMR
To a Schlenk flask charged with Grubbs’ catalyst 2 (0.42 g,
0.50 mmol) and CuCl (0.05 g, 0.50 mmol), compound 14 (or 15, 16)
(0.6 mmol) in 10 mL dry dichloromethane was added at room
temperature under N2. The resulting mixture was stirred for 40 min
at 40 ꢀC. After being cooled to room temperature, the reaction
mixture was filtered and the clear filtrate was collected. The solvent
from the filtrate was evaporated under vacuum to give a residue.
The residue was purified by silica gel chromatography (CH2Cl2:
ethyl acetate ¼ 2:1 or pentanes: ethyl acetate ¼ 3:2 or1:1) to give
the desired product as a green crystalline solid.
(400 MHz, CDCl3)
d
(ppm): 1.64 (d, J ¼ 6.7 Hz, 3H),1.90 (d, J ¼ 6.6 Hz,
3H), 2.95 (s, 3H), 3.08 (s, 3H), 4.91 (q, J ¼ 6.6 Hz, 1H), 6.20 (m, 1H),
6.72 (m, 2H), 6.90 (m, 1H), 7.10 (m, 1H), 7.42 (d, J ¼ 7.5 Hz, 1H). 13
C
NMR (100 MHz, CDCl3) d: 17.6, 18.9, 36.3, 36.5, 74.2, 112.4, 121.4,
125.4, 126.4, 126.5, 127.8, 130.1, 136.9, 153.8, 171.1 ppm. IR (KBr)
3071, 2930, 2917, 1662, 1488, 1455, 1396, 1241, 1115, 1071, 1038, 965,
747 cmꢁ1
n:
.
4.2.2. 2-(4-Methoxy-2-(prop-1-enyl)phenoxy)propanoic acid (15b)
Yellow oil. Yield: 64.2%. Analytical Data. Calcd (found) for
C
15H21NO3: C, 68.42 (68.45); H, 8.04 (8.09); N, 5.32 (5.36). 1H NMR
4.4.1. Catalyst 17a
(400 MHz, CDCl3)
d
(ppm): 1.61 (d, J ¼ 6.8 Hz, 3H), 1.92 (d,
Yield:
33H40Cl2N2O3Ru: C, 57.89 (57.65); H, 5.89 (5.72); N, 4.09 (4.01). 1H
NMR (400 MHz, CDCl3)
64.1%.
Analytical
Data.
Calcd
(found)
for
J ¼ 6.6 Hz, 3H), 2.96 (s, 3H), 3.09 (s, 3H), 3.8 (s, 3H), 4.88 (q,
C
J ¼ 6.7 Hz,1H), 6.21 (m,1H), 6.67 (m, 3H), 6.99 (d, J ¼ 2.9 Hz,1H). 13
C
d
(ppm): 1.20 (t, J ¼ 7.1 Hz, 3H), 1.52 (d,
NMR (100 MHz, CDCl3) d: 17.6, 18.9, 36.3, 36.5, 55.6, 74.8, 111.8,
J ¼ 6.7, 3H), 2.40 (bs, 6H), 2.50 (bs, 12H), 4.08 (q, J ¼ 7.0 Hz, 2H), 4.14
(s, 4H), 4.98 (q, J ¼ 6.7,1H), 6.65 (d, J ¼ 8.2 Hz,1H), 6.92 (m, 2H), 7.06
(s, 4H), 7.48 (t, J ¼ 6.8 Hz, 1H), 16.57 (s, 1H). 13C NMR (100 MHz,
112.6, 114.3, 125.3, 126.8, 128.6, 148.1, 154.3, 171.4 ppm. IR (KBr)
3080, 2934, 2846, 1660, 1581, 1492, 1428, 1212, 1084, 1039, 965, 915,
814 cmꢁ1
n:
.
CDCl3) d: 14.1, 17.4, 21.2, 51.7, 62.1, 73.3, 112.5, 122.8, 123.7, 128.8,
129.4, 138.2, 145.8, 151.2, 170.6, 210.4, 299.7 ppm. IR (KBr)
2918, 2858, 2735, 1938, 1728, 1593, 1574, 1479, 1450, 1410, 1295,
1224, 1115, 1088, 1043, 852, 750, 578 cmꢁ1
n: 3025,
4.2.3. 2-(4-Methyl-2-(prop-1-enyl)phenoxy)propanoic acid (15c)
.
Light yellow oil. Yield: 67.7%. Analytical Data. Calcd (found) for:
C
14H18O3 C, 71.77 (71.56); H, 7.74 (7.78) 1H NMR (400 MHz, CDCl3)
4.4.2. Catalyst 17b
Yield: 64.2%.
C34H42Cl2N2O4Ru: C, 57.14 (57.09); H, 5.92 (5.83); N, 3.92 (3.78). 1H
NMR (400 MHz, CDCl3)
d
(ppm): 1.65 (d, J ¼ 6.5 Hz, 3H), 1.94 (q, J ¼ 6.6 Hz, 3H), 2.29 (s, 3H),
Analytical
Data.
Calcd
(found)
for
2.95 (s, 3H), 3.09 (s, 3H), 4.90 (q, J ¼ 6.2 Hz, 1H), 6.01 (m, 1H), 6.65e
6.68 (m, 2H), 6.95 (m, 1H), 7.28 (d, J ¼ 6.8 Hz, 1H). 13C NMR
d
(ppm): 1.22 (t, J ¼ 6.7 Hz, 3H), 1.51 (d,
(100 MHz, CDCl3) d: 17.6, 18.9, 34.4, 36.3, 36.5, 73.9, 112.0, 115.1,
J ¼ 6.6, 3H), 2.41 (bs, 6H), 2.53 (bs, 12H), 3.76 (s, 3H), 4.09 (q,
J ¼ 7.0 Hz, 2H), 4.16 (s, 4H), 4.93 (q, J ¼ 6.6, 1H), 6.56 (t, J ¼ 6.8 Hz,
1H), 7.06 (s, 1H), 7.08 (s, 4H), 16.57 (s, 1H). 13C NMR (100 MHz,
126.1, 127.0, 127.2, 127.8, 130.6, 137.1, 153.1, 172.1 ppm. IR (KBr)
3061, 2934, 2933, 1661, 1455, 1444, 1366, 1234, 1110, 1061, 1044,
955, 733 cmꢁ1
n:
.
CDCl3)
129.4, 138.1, 145.3, 146.1, 156.0, 170.8, 210.2, 299.2 ppm. IR (KBr)
3091, 2974, 2916, 2735, 1940, 1724, 1606, 1590, 1488, 1443, 1413,
1306, 1257, 1124, 1087, 1034, 852, 784, 580 cmꢁ1
d: 14.1, 17.4, 21.1, 51.7, 55.8, 62.1, 73.3, 107.4, 112.7, 113.8,
n
:
4.3. General procedure for preparation of 16aed
.
A flask was charged with dry acetone (15 mL), K2CO3 (0.8 g,
6.0 mmol), 3-bromo-dihydrofuran-2-one (1.0 g, 6.0 mmol) and
13aed (4.0 mmol). Then, the reaction mixture was stirred for 4 h
under reflux. After cooling to room temperature, the mixture was
filtered and concentrated to afford a crude product. The crude
product was purified by silica gel chromatography (CH2Cl2).
4.4.3. Catalyst 17c
Yield: 62.6%.
33H39Cl2N3O5Ru: C, 54.32 (54.26); H, 5.39 (5.23); N, 5.76 (5.80). 1H
NMR (400 MHz, CDCl3)
(ppm): 1.21 (t, J ¼ 6.5 Hz, 3H), 1.53 (d,
J ¼ 6.3, 3H), 2.43 (bs, 6H), 2.49 (bs, 12H), 4.07 (q, J ¼ 7.1 Hz, 2H), 4.17
Analytical
Data.
Calcd
(found)
for
C
d

8
Y. Zhang et al. / Journal of Organometallic Chemistry 756 (2014) 1e9
(s, 4H), 5.04 (q, J ¼ 6.7, 1H), 6.75 (d, J ¼ 8.9 Hz, 1H), 7.09 (s, 4H), 7.84
(s, 1H), 8.43 (d, J ¼ 8.9 Hz, 1H), 16.47 (s, 1H). 13C NMR (100 MHz,
4.5. Kinetics study of 17, 18 and 19
CDCl3)
d
: 14.1, 17.3, 21.1, 51.6, 62.6, 74.5, 112.6, 117.2, 123.4, 129.5,
A Schlenk flask was charged with catalyst (0.02 mmol, 1.0 mol%)
and CH2Cl2. The sample was equilibrated at 30 ꢀC (or 0 ꢀC) before
diethyl diallylmalonate 20 (or diallyltosylamide 22) was added via a
syringe. Aliquots were taken from the reaction mixture at the
appropriate times using a syringe and were quenched immediately
with 0.1 mol/L PEI in CH2Cl2. The resulting solution was then sub-
jected to short column chromatography to remove the Ru metal
residue using CH2Cl2 as the eluent. The solvent from the collected
solution was evaporated under vacuum. The conversion yield to
substrates was determined by comparing the ratio of the integrals
of the 1H NMR methylene proton peaks in the starting material
with those in the product. The results are shown in Figs. 3e5.
138.7, 144.2, 145.2, 154.9, 169.8, 207.3, 294.0 ppm. IR (KBr)
2916, 2738, 1942, 1728, 1605, 1573, 1520, 1479, 1415, 1341, 1263,
1231, 1136, 1089, 1043, 907, 856, 744 cmꢁ1
n: 3085,
.
4.4.4. Catalyst 17d
Yield: 67.7%.
34H42Cl2N2O3Ru: C, 58.45 (58.29); H, 6.06 (6.01); N, 4.01 (4.05). 1H
NMR (400 MHz, CDCl3)
Analytical
Data.
Calcd
(found)
for
C
d
(ppm): 1.23 (t, J ¼ 7.1 Hz, 3H), 1.52 (d,
J ¼ 6.6, 3H), 2.39 (s, 3H), 2.43 (bs, 6H), 2.53 (bs, 12H), 4.09 (q,
J ¼ 6.7 Hz, 2H), 4.13 (s, 4H), 4.95 (q, J ¼ 6.7, 1H), 6.55 (d, J ¼ 8.3 Hz,
1H), 6.76 (s, 4H), 7.10 (s, 4H), 7.30 (d, J ¼ 8.4 Hz,1H),16.42 (s,1H). 13
C
NMR (100 MHz, CDCl3) d: 14.3, 17.6, 21.4, 27.4, 51.9, 62.3, 73.4, 112.3,
129.5, 129.4,129.6,133.1, 138.4,145.9,149.5,171.0, 210.6, 300.1 ppm.
IR (KBr) : 3034, 2922, 2855, 2735, 1945, 1724, 1486, 1446, 1407,
1257, 1217, 1139, 1103, 1044, 854, 581 cmꢁ1
4.6. Catalytic study of the ruthenium carbenes 17, 18 and 19
n
.
The general procedure for metathesis reactions with ruthenium
carbenes 17, 18 and 19 was performed as follows: a certain amount
of ruthenium carbene catalyst 17 (or 18, or 19) (0.0005 mmol) and a
solution of the substrate in 1.0 mL dry CH2Cl2 (or toluene) was
mixed in a reaction flask under nitrogen. The reaction mixture was
stirred for 0.3e24 h. At the end of the reaction (monitored by thin-
layer chromatography (TLC)), the catalysts were separated by silica
gel chromatography using CH2Cl2 as the eluent to remove trace
amounts of Ru residues. Conversions were estimated by 1H NMR
spectroscopy and obtained by comparing the ratios of the integrals
of the starting materials with those of products. The catalytic ac-
tivities of ruthenium carbene 17,18 and 19 for a variety of substrates
are shown in Table 3.
4.4.5. Catalyst 18a
Yield: 66.8%.
33H41Cl2N3O2Ru: C, 57.97 (57.60); H, 6.04 (6.10); N, 6.15 (6.08). 1H
NMR (400 MHz, CDCl3)
Analytical
Data.
Calcd
(found)
for
C
d
(ppm): 1.47 (d, J ¼ 6.4 Hz, 3H), 2.39 (bs,
6H), 2.51 (bs, 12H), 2.81 (s, 3H), 2.89 (s, 3H), 4.10 (s, 4H), 5.23 (q,
J ¼ 6.6, 1H), 6.74 (d, J ¼ 8.0 Hz, 1H), 6.94 (t, J ¼ 6.4 Hz, 2H), 7.06 (s,
4H), 7.48 (t, J ¼ 6.3 Hz, 1H), 16.49 (s, 1H). 13C NMR (100 MHz, CDCl3)
d
: 16.8, 21.1, 36.3, 36.9, 51.8, 71.9, 112.8, 122.7, 12.7, 129.3, 137.8,
138.8, 147.1, 151.0, 170.2, 211.1, 302.5 ppm. IR (KBr)
2943, 2915, 2735, 1992, 1625, 1477, 1406, 1294, 1258, 1208, 1107,
1040, 852, 749, 508 cmꢁ1
n: 3070, 3033,
.
4.4.6. Catalyst 18b
Yield: 65.2%.
34H43Cl2N3O3Ru: C, 57.22 (57.05); H, 6.07 (6.04); N, 5.89 (5.65). 1H
NMR (400 MHz, CDCl3)
Acknowledgments
Analytical
Data.
Calcd
(found)
for
C
Financial supports from the National Science Foundation of
China (NSFC 21102102, 21072149, and 20872108) are gratefully
acknowledged.
d
(ppm): 1.38 (d, J ¼ 6.4 Hz, 3H), 2.41 (bs,
6H), 2.54 (bs,12H), 2.75 (s, 3H), 2.77 (s, 3H), 3.77 (s, 3H), 4.10 (s, 4H),
5.22 (q, J ¼ 6.6, 1H), 6.50 (s, 1H), 6.76 (d, J ¼ 8.7 Hz, 2H), 7.02 (d,
J ¼ 6.3 Hz, 1H), 7.08 (s, 4H), 16.33 (s, 1H). 13C NMR (100 MHz, CDCl3)
Appendix A. Supplementary data
d: 16.7, 21.1, 36.2, 37.0, 51.7, 60.3, 71.9,107.0,113.6,129.3,137.7,138.8,
145.0, 147.5, 156.0, 170.6, 210.9, 301.5 ppm. IR (KBr)
2735, 1947, 1634, 1486, 1409, 1259, 1210, 1155, 1097, 1075, 1037, 912,
854, 731, 581 cmꢁ1
n: 3033, 2918,
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.01.017.
.
4.4.7. Catalyst 19a
Yield: 64.0%.
32H36Cl2N2O3Ru: C, 57.48 (57.41); H, 5.43 (5.35); N, 4.19 (4.15). 1H
NMR (400 MHz, CDCl3) (ppm): 2.41 (bs, 6H), 2.45 (bs, 12H), 2.57e
References
Analytical
Data.
Calcd
(found)
for
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C
d
(b) P. Schwab, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc. 118 (1996) 100;
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2.64 (m, 2H), 4.13 (s, 4H), 4.25e4.30 (m, 1H), 5.15 (q, J ¼ 6.6, 1H),
6.91 (m, 2H), 7.07 (d, J ¼ 7.0, 4H), 7.28 (s, 1H), 7.54 (t, J ¼ 7.2 Hz, 1H),
16.52 (s, 1H). 13C NMR (100 MHz, CDCl3)
d: 21.1, 29.1, 51.5, 65.4, 73.3,
107.0, 114.6, 114.7, 129.4, 138.8, 144.5, 146.0, 156.1, 171.5, 209.6,
294.7 ppm. IR (KBr) : 2951, 2917, 2735,1938,1785,1688,1595,1574,
1408, 1424, 1398, 1264, 1215, 1175, 1134, 1020, 993, 747, 577 cmꢁ1
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Yield: 64.2%.
33H38Cl2N2O4Ru: C, 56.73 (56.61); H, 5.48 (5.25); N, 4.01 (3.96). 1H
NMR (400 MHz, CDCl3) (ppm): 2.40 (bs, 6H), 2.45 (bs, 12H), 2.52
Analytical
Data.
Calcd
(found)
for
C
(d) K.C. Nicolaou, P.G. Bulger, D. Sarlah, Angew. Chem. Int. Ed. 44 (2005) 4490;
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4865;
d
(m, 2H), 3.74 (s, 3H), 4.03 (q, J ¼ 7.4, 1H), 4.19 (s, 4H), 4.26 (q, J ¼ 6.6,
1H), 5.06 (t, J ¼ 6.84, 1H), 6.44 (s, 1H), 7.07 (d, J ¼ 6.8, 4H), 7.11 (s,
4H), 7.18 (d, J ¼ 8.9 Hz, 1H), 16.41 (s, 1H). 13C NMR (100 MHz, CDCl3)
(f) T.J. Donohoe, A.J. Orr, M. Bingham, Angew. Chem. Int. Ed. 45 (2006) 2664;
(g) A. Fürstner, Angew. Chem. Int. Ed. 39 (2000) 3013;
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138.7, 144.1, 151.7, 171.3, 209.8, 295.5 ppm. IR (KBr)
236, 2059, 1950, 1783, 1631, 1604, 1587, 1487, 1422, 1261, 1210, 1175,
1031, 917, 854, 580 cmꢁ1
n: 2916, 2860,
(c) M. Benaglia, A. Puglisi, F. Cozzi, Chem. Rev. 103 (2003) 3401;
(d) N.E. Leadbeater, M. Marco, Chem. Rev. 102 (2002) 3217;
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