Synthesis and Evaluation of Ruthenium 2-Alkyl-6-mercaptophenolate Catalysts for Olefin Metathesis

Article abstract of DOI:10.1002/aoc.4939

A series of ruthenium carbene catalysts containing 2-sulfidophenolate bidentate ligand with an ortho-substituent next to the oxygen atom were synthesized. The molecular structure of ruthenium carbene complex containing 2-isopropyl-6-sulfidophenolate ligand was confirmed through single crystal X-ray diffraction. An oxygen atom can be found in the opposite position of the N-heterocyclic carbene (NHC) based on the steric hindrance and strong trans-effects of the NHC ligand. The ruthenium carbene catalyst can catalyze ring-opening metathesis polymerization (ROMP) reaction of norbornene with high activity and Z-selectivity and cross metathesis (CM) reactions of terminal alkenes with (Z)-but-2-ene-1,4-diol to give Z-olefin products (Z/E ratios, 70:30–89:11) in low yields (13%–38%). When AlCl₃ was added into the CM reactions, yields (51%–88%) were considerably improved and process becomes highly selective for E-olefin products (E/Z ratios, 79:21–96:4). Similar to other ruthenium carbene catalysts, these new complexes can tolerate different functional groups.

Full text of DOI:10.1002/aoc.4939

Received: 29 January 2019
DOI: 10.1002/aoc.4939
Revised: 14 March 2019
Accepted: 14 March 2019
F U L L P A P E R
Synthesis and Evaluation of Ruthenium 2‐Alkyl‐6‐
mercaptophenolate Catalysts for Olefin Metathesis
Tao Wang1,2
| Xiaobo Yu3 | Huiqing Zhang1,2 | Shutao Wu1,2 | Weijie Guo1,2
|
Jianhui Wang1,2
1 Department of Chemistry, College of
Science, Tianjin University, Tianjin
300350, People's Republic of China
2 Collaborative Innovation Center of
Chemical Science and Engineering
(Tianjin), 30072, People's Republic of
China
3 College of Materials Science and
Engineering, Jilin Institute of Chemical
Technology, Jilin City 132022, People's
Republic of China
A series of ruthenium carbene catalysts containing 2‐sulfidophenolate
bidentate ligand with an ortho‐substituent next to the oxygen atom were syn-
thesized. The molecular structure of ruthenium carbene complex containing
2‐isopropyl‐6‐sulfidophenolate ligand was confirmed through single crystal
X‐ray diffraction. An oxygen atom can be found in the opposite position of
the N‐heterocyclic carbene (NHC) based on the steric hindrance and strong
trans‐effects of the NHC ligand. The ruthenium carbene catalyst can catalyze
ring‐opening metathesis polymerization (ROMP) reaction of norbornene with
high activity and Z‐selectivity and cross metathesis (CM) reactions of
terminal alkenes with (Z)‐but‐2‐ene‐1,4‐diol to give Z‐olefin products (Z/E
ratios, 70:30–89:11) in low yields (13%–38%). When AlCl3 was added into the
CM reactions, yields (51%–88%) were considerably improved and process
becomes highly selective for E‐olefin products (E/Z ratios, 79:21–96:4). Similar
to other ruthenium carbene catalysts, these new complexes can tolerate differ-
ent functional groups.
Correspondence
Jianhui Wang, Department of Chemistry,
College of Science, Tianjin University,
Tianjin 300350, People's Republic of
China.
Email: wjh@tju.edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Numbers: 21372175,
21572155 and JJKH20180554KJ
KEYWORDS
AlCl3, olefin metathesis, ortho‐substituent, ruthenium carbene catalysts, Z/E‐selective
1 | INTRODUCTION
catalyst has been used to promote RCM reaction to
form 45‐membered macrocyclic compounds with
Olefin metathesis reaction is an efficient and fast method
for rapid building of complex molecules and macromole-
cules. Stereogenic‐at‐metal complexes have been a popu-
lar research area in olefin metathesis reactions.[1,2] At
present, generation of cis‐olefin products through cata-
lytic reactions has attracted considerable attention in
the olefin metathesis reaction field. Complexes of molyb-
denum,[3–5] tungsten,[6,7] and ruthenium[8–11] have been
developed to obtain cis‐olefin metathesis products. For
example, a series of molybdenum complexes with
monopyrrolide aryloxide ligands have been synthesized
and utilized for enantioselective ring closing (RCM),[12]
ring opening/cross (ROCM),[4] or cross (CM)[13] metathe-
ses to obtain Z‐olefin products. A tungsten oxo alkylidene
Z‐selectivity.[7] Ruthenium complexes with specific struc-
tures have attracted considerable research attention as
these catalysts have good functional group tolerance. Also
some new structures of ruthenium carbene complexes
with good Z‐selectivity have been developed. In 2011,
Grubbs et al. reported a Z‐selective Ru olefin metathesis
catalyst 1a that contained a N‐heterocyclic carbene
(NHC) bidentate ligand (Figure 1, 1a).[11] Further
studies have shown that complex 1a has high selectivity
for Z‐olefins in a variety of CM reactions. In 2012, a
ruthenium‐based olefin metathesis catalyst 1b
(Figure 1, 1b) was developed and used for CM reactions
with good activity and excellent Z‐selectivity.[14] Subse-
quently, catalyst 1b was applied to generate macrocyclic
Appl Organometal Chem. 2019;e4939.
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https://doi.org/10.1002/aoc.4939

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WANG ET AL.
in the activity (the pKa values of ligands shown in
Figure 2, b), but the pKa values of L1‐L3 are very close,
which indicates that the steric hindrance of ligands is
the most important factor affecting the stability and activ-
ity of the catalysts formed by these three ligands.
Therefore, we designed and synthesized a set of cata-
lysts with large steric hindrance at ortho‐oxygen sites.
Thus, the position of the oxygen atom is fixed at trans
position to the NHC. We investigated effects of steric hin-
drance and electronic effects on the catalytic performance
of the catalysts, and the activity and selectivity of ROMP
and CM reactions of Z‐olefins and terminal olefins are
also studied.
FIGURE 1 Catalysts used previously to generate predominant
Z‐products
lactones, lactams, and ketones containing cis‐olefin frame-
work with the purpose of synthesizing pheromones and
fragrances.[15] Catalyst 2a (Figure 1) was reported by
Hoveyda and co‐workers in 2013 and used for ROCM or
ROMP reactions of substrate with highly strained cyclic
olefins to obtain a Z‐product.[16] In 2015, catalyst 2b bear-
ing a benzene‐1,2‐dithiolate ligand with 3,6‐dichloro sub-
stituents was reported by Hoveyda group, and exhibited
high activity and selectivity for CM reactions of Z‐olefins
and terminal olefins.17a Besides, complex 2b also could be
used for RCM reactions with Z‐selectivity.17b, c In 2016,
catalysts 3 and 4 were reported for ROMP reaction of
norbornene. They exhibited very high catalytic activity
(>98%) but lower selectivity (61%–67%).[18]
In 2015, Hoveyda proposed a possible decomposition
mechanism of dithiolate chelated catalyst, which is
showed in the Figure 2, a.[17] Deactivation of the catalysts
is caused by the interaction of sulfur atom trans to the
NHC ligand with carbene center. Sulfur atom has a
strong nucleophilicity, if the sulfur atom coordinated
trans to the NHC ligand is replaced by less nucleophilic
atom, the decomposition may be reduced. Catalysts 3
and 4[18] were obtained by replacing one of the sulfur
atoms of the disulfide ligand with oxygen atom. In the
catalyst, although the oxygen atom favored to be coordi-
nated trans to the NHC due to the trans effect[19] of the
ligand, position of the oxygen and sulfur atom can be
reversed. When a large substituent group is added to the
ortho‐position of the oxygen atom, it would control the
coordination geometry. In addition to the steric effect of
ligands, electronic effects may also play an important role
2 | RESULTS AND DISCUSSION
New Ru complexes containing a 2‐R‐6‐sulfidophenolate
ligand could be synthesized via pathways, shown at
Scheme 1. First, 2‐mercapto‐6‐R‐phenol ligands were syn-
thesized according to the process described in previous
studies with slight modifications. Thus, 2‐R‐phenol (6a,
R = Me; 6b, R = i‐Pr; 6c, R = t‐Bu) was reacted with
NaH in DMF to obtain the corresponding sodium salt.
After the reaction was completed, N, N‐dimethylami-
nothioformyl chloride (A1) (1.2 equiv) was added into
the reaction mixture at −10 °C, and then the reaction
mixture temperature was raised to 80 °C for 1 hr. After
completion, silica gel column purified the crude product
to obtain O‐(o‐R‐phenyl)dimethylcarbamothioate (7a,
R = Me; 7b, R = i‐Pr; 7c, R = t‐Bu). The corresponding
7‐R‐benzo[d][1,3]oxathiol‐2‐one products (8a, R = Me;
8b,
R
=
i‐Pr; 8c,
R
=
t‐Bu) were formed via
in the
intramolecular oxidative cyclization of
7
presence of p‐benzoquinone under the catalysis of Pd
(OAc)2 (5.0 mol%) and p‐toluenesulfonic acid
(10 mol%).[20] 2‐Mercapto‐6‐R‐phenol ligands (9a,
R = Me; 9b, R = i‐Pr; 9c, R = t‐Bu) were then obtained
via hydrolysis of 8 with an aqueous solution of NaOH in
ethanol. The total yields from the starting phenols
were 33%, 24%, and 20% for 9a, 9b, and 9c, respectively.
2‐Mercapto‐6‐R‐phenol ligands were then converted to
the corresponding zinc salts 10a (R = Me), 10b (R = i‐Pr)
and 10c (R = t‐Bu) in the yields of 67%, 48%, and 52%,
respectively. These zinc salts 10 were treated with the
Grubbs–Hoveyda II catalyst in THF at room temperature
to obtain the desired products 11a, 11b and 11c in yields
1
of 78%, 71%, and 81%, respectively. The H NMR spectra
of the obtained complexes contained singlet peaks
at values of δ15.58, δ15.56, and δ15.61 ppm, which corre-
spond to the benzylidene protons of complexes 11a, 11b
and 11c, respectively, thereby indicating successful
exchange of ligands.
FIGURE 2 Possible pathway for catalyst decomposition (top) and
the pKa values of the ligands (bottom)

WANG ET AL.
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SCHEME 1 Synthesis of ruthenium carbene catalysts 11a, 11b and 11c
A single crystal of the complex 11b was grown by
slow evaporation from CH2Cl2/n‐hexane mixture solution
at −18 °C under N2. The structure of 11b was determined
using X‐ray diffraction, as shown in Figure 3. Arrange-
ment of the ligands around the metal center is similar
to that found in Hoveyda complexes. Compound 11b
has a slightly deformed trigonal bipyramidal structure
with NHC carbene, one sulfide and one oxide, the phenyl
oxide, and the benzylidene carbene ligand seated around
the Ru metal center. The presence of a large sterically
hindered group in the ortho position of the phenolic oxy-
gen causes the oxygen atom to be in the position to the
NHC carbene.
The complex contains sulfur and oxygen chelating
ligands with large steric hindrance at the ortho position
in combination with a ruthenium metal center. In this
configuration, phenolic oxygen occupies the trans‐
position with the NHC ligand due to the synergistic effect
of steric hindrance. As sulfur and oxygen chelating
ligands have large sterically hindered substituents, repul-
sive forces between thiophenol and NHC ligand can be
increased, thereby forcing the ligand to be as far away
as possible from the NHC.
To study effect of substituents thermal stability of the
catalyst was tested in CDCl3 at 30 °C and in DMSO‐d6
50 °C, and trend of the decomposition was shown in
Figure 4. When CDCl3 is used as a solvent, complexes
11a‐c will convert to Grubbs–Hoveyda II catalyst when
heated to 50 °C. Hoveyda and his co‐workers observed
a similar phenomenon,21a which could be caused by
the decrease in stability of the Ru − O bond due to
the high temperature. When oxygen and sulfur atoms
dissociated, Ru binds with chloride ions from CDCl3 to
form Grubbs‐Hoveyda II catalyst.21b Figure 4 shows sta-
bility of the catalyst at 50 °C is much lower than at
30 °C. Changing the ortho‐substituent of oxygen has a
significant effect on the catalysts. Ortho‐isopropyl‐
substituted complex 11b is more stable than ortho‐
substituted methyl‐ or t‐butyl‐substituted complexes
11a or 11c, and the stability of the ortho‐t‐butyl
substituted complex is the lowest. In the first hours
decomposition rate of complexes 11a‐c are very high.
FIGURE 3 Crystal structure of 11b.
Displacement ellipsoids are drawn at 50%
of probability

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WANG ET AL.
FIGURE 4 Stability of complexes 11a‐c
in CDCl3 at 30 °C and DMSO‐d6 at 50 °C
under N2. Internal standard was
benzophenone and reactions were
1
monitored by H NMR
Then, the decomposition rate slows down gradually
until it is completed.
reaction of norbornene catalyzed by complexes 11a‐c, it
seems that the change of the hindrance of ortho‐
substituents affects the catalytic activity of the catalyst,
but has no obvious effect on the selectivity. When an
equivalent of AlCl3 was added to the complex 11b, so‐
formed product exhibited extremely high catalytic activity.
Amount of complex 11b was only 10% of the previous, but
a higher yield was obtained. However, the product is
mainly trans olefin (E/Z: 92:8). When amount of the cata-
lyst was reduced to only 0.005 mol%, the turnover number
(TON) of the product reached 4700.
Then, three terminal olefins were used for CM reac-
tions with (Z)‐but‐2‐ene‐1,4‐diol using complexes 11a to
11c, and catalytic activity and selectivity are shown in
Table 2. CM reactions were obtained in THF at 22 °C in
the presence of complexes 11a to 11c (5.0 mol%) under
N2. These catalysts are mainly selective for Z‐olefin prod-
ucts (Z/E 70:30–88:12), but yields were very low (13% to
35%). Compared with catalysts 11b and 11c, catalyst 11a
is more Z‐stereoretentive, but gives lower yields. Catalyst
11c has the largest steric hindrance in the ortho‐position
but is inferior to catalyst 11b in terms of yields and selec-
tivities. These results are mainly due to the combined
effects of steric hindrance and electronic effects. Thus,
catalyst 11b was chosen to catalyze different terminal ole-
fins. To increase the catalytic activity of the catalyst, we
added Lewis acid (AlCl3) into the system. The addition
of AlCl3 greatly enhanced the activities of catalyst 11b,
but switched selectivity toward E‐olefin products. The
mechanism action of AlCl3 is still under study and rele-
vant reports will be presented in subsequent articles. Sim-
ilar to other Ru‐based olefin metathesis catalysts, these
Catalytic activity and Z‐selectivity of complexes 11a‐c
for ROMP reaction of norbornene were tested and results
are shown in Table 1. ROMP reactions in CH2Cl2 at
22 °C in the presence of complexes 11a to 11c (1.0 mol%)
under N2 proceeded smoothly to obtain a polymer
product. Complexes 11a‐c have high activities (78%, 87%
and 82%) and demonstrate medium Z‐selectivity (Z/
E = 75:25). Complexes 11a‐c gave lower yields than those
of 3 and 4 (>98%) but displayed higher Z‐selectivity (Z/E:
61% (3), 67% (4)).[18] This indicated that increase of substit-
uent at the ortho‐position of the oxygen atom remarkably
reduces the activity of the catalyst but effectively improves
selectivity of the catalyst. From the results of ROMP
TABLE 1 Study of Ru‐based complexes catalytic ROMP of
norbornenea,b,c
entry complex; mol% AlCl3/mol% yield Z/E TON
1
2
3
4
5
11a; 1.0
11b; 1.0
11c; 1.0
11b; 0.1
11b; 0.005
‐‐‐
‐‐‐
‐‐‐
78% 75:25
87% 75:25
82% 75:25
78
87
82
0.1
0.005
86%
22%
8:92
860
7:93 4700
aROMP reactions were performed under N2 atmosphere; Time: 1 hr;
bYields refer to the average value obtained for at least three runs;
cZ:E ratios of the products were determined by analysis of the 1H NMR
spectra.

WANG ET AL.
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TABLE 2 Selectivity study of catalyst 11a, 11b and 11c in cross metathesisa,b,c
Product
Catalyst
13
14
15
11a
11b
11c
19% yield; Z/E:77:23
28% yield; Z/E:79:21
23% yield; Z/E:70:30
13% yield; Z/E: 86:14
22% yield; Z/E: 83:17
18% yield; Z/E: 80:20
27% yield; Z/E: 88:12
35% yield; Z/E: 86:14
30% yield; Z/E: 84:16
aReaction duration: 6 hr; Solvent: THF (0.5 ml); r.t.; Ru complex: 5 mol%; Terminal alkenes: 1.0 equiv.; (Z)‐but‐2‐ene‐1,4‐diol: 2.0 equiv., under N2;
bZ/E were determined by analysis of 1H NMR spectra of the mixtures;
cYields are based on isolated products.
TABLE 3 Selectivity study of catalyst 11b with AlCl3 in cross metathesisa,b,c
13,
15,
95(88)%; Z/E:11:89
83(77)%; 10:90
14, 96(87)%; 9:91
16, 57(51)%; 7:93
18,
20,
17, 93(84)%; 4:96
69(63)%; 10:90
72(66)%; 6:94
No AlCl3. 20(19)%; 80:20
No AlCl3 41(38)%;89:11
19, 79(71)%; 5:95
22,
58(51)%; 21:79
21, 81(75)%; 8:92
aReaction duration: 6 hr; Solvent: THF (0.5 ml); r.t.; Ru complex: 5 mol%; AlCl3: 5 mol%; Terminal alkenes: 1.0 equiv.; (Z)‐but‐2‐ene‐1,4‐diol: 2.0 equiv.;
under N2;
bConversions and Z/E were determined by analysis of 1H NMR spectra of the mixtures;
cYields are based on isolated products.
catalysts tolerate many different functional groups. For
example, CM occurred between (Z)‐but‐2‐ene‐1,4‐diol
and terminal alkenes with nitro (13), ketone (14 and 16)
and unprotected amino (19) groups. In addition, CM reac-
tion was successful for olefins with different chain lengths
(15, 17 and 18), and longer chains gave higher yields (con-
trary to the results when AlCl3 was added) (Table 3).
new structures, phenoxy oxygen occupies trans‐position
to the NHC ligand due to the synergetic effect of the steric
hindrance. Such Ru‐carbene complexes containing a
large sterically hindered 2‐sulfidophenolate chelating
ligand have different substituents at the ortho position
of phenolic oxygen that have an enhanced effect on the
stability of the compound, and the order of the catalyst
stability is ‐i‐Pr > −Me> − t‐Bu. The series of catalysts
can catalyze ROMP reaction of norbornene with high
yields, and Z‐selectivity (75%). When AlCl3 was added,
the activities of the catalysts were greatly improved. The
products are mainly E‐selective (E/Z 79:21 to 96:4) giving
products in moderate to good yields (51–88%). In addi-
tion, this work provides a theoretical basis for the
3 | CONCLUSIONS
A series of 2‐sulfidophenolate chelated Ru carbene cata-
lysts 11a to 11c were synthesized, thus obtaining new
structures previously unknown in the literature. In the

6 of 10
WANG ET AL.
synthesis and design of other stable and efficient metal
catalysts. Furthermore, studies on increasing catalytic
activity and changing the selectivity by adding AlCl3 are
currently being performed in our laboratories.
After the reaction was completed, it was poured into a
200 ml KOH (1%) solution, and extracted with ethyl
acetate (3 x 50 ml). Combined the organic layer, washed
with water (100 ml) and dried with anhydrous MgSO4.
It was purified by column chromatography (ethyl
acetate: petroleum ether (1:20)) to provide a yellow solid
4 | EXPERIMENTAL
4.1 | General information
1
(10.93 g, yield 56%). H NMR (400 MHz, CDCl3) δ 7.23
(t, J = 7.5 Hz, 2H), 7.19–7.12 (m, 1H), 6.98 (d, J = 7.7 Hz,
1H), 3.46 (s, 3H), 3.35 (s, 3H), 2.20 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3) δ 187.24, 152.60, 130.96, 126.78,
126.13, 123.04, 43.31, 38.59, 16.38 ppm.
Unless otherwise noted, all reactions were performed
under an atmosphere of dry N2 with oven‐dried glassware
and anhydrous solvents with standard dry box or vacuum
line techniques. The starting products were synthesized
according to the literatures (1‐(but‐3‐en‐1‐yloxy)‐4‐nitro-
benzene,[22] N‐(5‐hexenyl)phthalimide,[23] 5‐hexenyl ben-
4.2.2 | 7‐Methylbenzo[d][1,3]oxathiol‐2‐
one (8a)[20]
zoate,[24]
1‐[4‐hydroxy‐3‐(2‐propen‐
1‐yl)phenyl]
Added 7a (10 mmol, 1.95 g), Pd (OAc)2 (2.5 mmol, 0.56 g),
BQ (55 mmol, 5.95 g), TsOH (5 mmol, 0.95 g), glacial acetic
acid (30 ml) and toluene (30 ml) into a 100 ml flask, reflux
for 12 hr. After the reaction was completed, it was cooled
to room temperature and concentrated under reduced
pressure. This was purified by column chromatography
(ethyl acetate: petroleum ether (1:50)) to provide white
solid (1.38 g, yield 83%). 1H NMR (400 MHz, CDCl3)
δ 7.21 (d, J = 3.5 Hz, 1H), 7.13 (d, J = 3.2 Hz, 2H), 2.39
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 168.94,
146.86, 128.95, 124.97, 122.65, 119.70, 15.88 ppm.
ethanone,[25] 2‐propenyl benzoate,[26] 10‐undecenyl ben-
zoate,[27] N‐allyl‐4‐nitroaniline,[28] but‐3‐en‐1‐yl methyl
terephthalate,[26] 1‐bromo‐2‐(but −3‐en‐1‐yloxy)ben-
zene,[22] 4‐(hex‐5‐en‐1‐yloxy) benzonitrile.[22] All other
reagents and solvents were purchased were used as
received from commercial sources. All reactions in non‐
aqueous solvents were carried out under nitrogen in dried
glassware. Solvents were purified and dried as follows:
diethyl ether and hexane were distilled from sodium; tetra-
hydrofuran and toluene were distilled from sodium and
1
benzophenone. H and 13C NMR data were recorded on
400 MHz spectrometer with CDCl3 as solvent. The chemi-
cal shifts are reported in ppm relative to CDCl3 (δ = 7.26)
4.2.3 | 2‐Mercapto‐6‐methylphenol (9a)[29]
1
for H NMR and relative to the central CDCl3 resonance
(δ = 77.0) for 13C NMR. Coupling constants (J) are quoted
in Hz for 1H. Multiplicities are reported as follows: singlet
(s), doublet (d), doublet of doublets (dd), triplet (t), quartet
NaOH (3 mmol, 120.1 mg) was dissolved in 2 ml of water
and added slowly into 2 ml of ethanol contain 8a (1 mmol,
166.3 mg). It was stirred at 60 °C for 1 hr and then acid-
ified at 0 °C. 9a was extracted with ethyl acetate and dried
over anhydrous MgSO4. Ethyl acetate was removed under
vacuum, and the product was gain as a yellow oil
(99.5 mg, yield 71%). 1H NMR (400 MHz, CDCl3) δ
7.27 (d, J = 7.7 Hz, 1H), 7.06 (d, J = 7.4 Hz, 1H),
6.72 (t, J = 7.6 Hz, 1H), 6.27 (s, 1H), 2.90 (s, 1H), 2.25
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ 154.80,
133.33, 131.95, 124.57, 120.27, 110.94, 16.49 ppm.
1
(q), and multiplet (m). Conversions were obtained by H
NMR analysis of the sample. NMR data of known com-
pounds is in agreement with literature values. Infrared
spectra were recorded on FT‐IR spectrophotometer.
High‐resolution mass spectra (HRMS) were obtained on a
JEOL JMS‐DX303 instrument. The yields of the products
were determined by isolated products.
4.2 | Preparation of catalysts
4.2.1 | O‐(o‐tolyl) dimethylcarbamothioate
4.2.4 | O‐(2‐Isopropylphenyl)
(7a)[20]
dimethylcarbamothioate (7b)[20]
2‐Methylphenol (0.1 mol, 10.80 g) was dissolved in
DMF(100 ml) and added dropwise in NaH (0.12 mol,
4.81 g, 60% dispersion in mineral oil), stirred 1 hr in room
temperature. After that, it was cooled to 10 °C, N,N‐
dimethylaminothioformyl chloride (A1) (0.12 mol,
14.93 g) was added at once and stirred at 80 °C for 1 hr.
The synthesis method is the same as that of 7a and it was
purified by column chromatography to provide yellow
oil (yield 51%). 1H NMR (400 MHz, CDCl3) δ 7.33
(d, J = 7.2 Hz, 1H), 7.26–7.16 (m, 2H), 6.98 (d,
J = 7.2 Hz, 1H), 3.45 (s, 3H), 3.34 (s, 3H), 3.01 (dt,
J = 13.5, 6.8 Hz, 1H), 1.23 (d, J = 6.9 Hz, 6H) ppm. 13C

WANG ET AL.
7 of 10
NMR (100 MHz, CDCl3) δ 187.90, 151.40, 140.82, 126.62–
126.27, 123.43, 43.34, 38.65, 27.26, 23.14 ppm.
4.2.9 | Preparation of zinc salt (10a‐c)
Zn (OAc)2•2H2O (6.1357 g, 27.95 mmol, 3.3 equiv.) and 2‐
mercapto‐6‐methylphenol (1.19 g, 8.47 mmol, 1.0 equiv.)
were dissolved in i‐PrOH (20 ml). Ethylenediamine
(3.05 g, 50.82 mmol, 6.0 equiv.) was added to the solution,
and the resulting mixture is allowed to stir for 1 hr at 22 °C.
The precipitated solid was filtered, washed with methanol
(10.0 ml) and hot chloroform (10.0 mL), and dried in a
vacuum to afford zinc 2‐mercapto‐6‐methylphenol (10a)
(1.15 g, 5.67 mmol, 67% yield) as white solid. 10b and 10c
were synthesized in the same method.
4.2.5 | 7‐Isopropylbenzo[d][1,3]oxathiol‐2‐
one (8b)[20]
The synthesis method is the same as that of 8a and it was
purified by column chromatography to provide yellow oil
(yield 77%). 1H NMR (400 MHz, CDCl3) δ 7.20 (d,
J = 6.0 Hz, 3H), 3.35–3.17 (m, 1H), 1.29 (dd, J = 10.6,
6.9 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3) δ 168.81,
145.81, 133.31, 125.31, 124.86, 122.72, 119.71, 28.90,
22.32 ppm.
4.2.10 | Preparation of Ru‐based dithiolate
complex (11a)
Under N2 atmosphere, Grubbs‐Hoveyda II (250 mg,
0.40 mmol, 1 equiv.) and 10a (120 mg, 0.59 mmol, 1.5
equiv.) were added into a 2‐dram vial charged with a stir
bar, 5 ml THF was added at 0 °C. The resulting mixture
was allowed to stir at 6 °C for 1 hour, and then the solvent
was centrifuged under N2. After collecting the solution, it
was drained to a solid, and the solid was washed with
dry ether (3 x 5 ml) and dried. The product was pure
enough and without further purification. Ru‐Based com-
plex (11a) obtained as orange‐brown solid (216 mg,
0.31 mmol, 78% yield). Ru‐complex 11a: 1H NMR
(400 MHz, CDCl3) δ 15.61 (s, 1H), 7.31 (t, J = 6.6 Hz,
1H), 7.20 (d, J = 6.8 Hz, 1H), 7.11 (d, J = 7.6 Hz, 1H),
7.02 (s, 2H), 6.87 (d, J = 6.6 Hz, 1H), 6.59 (s, 3H), 6.45 (d,
J = 6.8 Hz, 2H), 5.23–5.08 (m, 1H), 3.87 (s, 4H), 2.45 (s,
6H), 2.30 (s, 9H), 2.06 (s, 3H), 1.61 (d, J = 4.7 Hz, 3H),
1.29 (s, 3H), 1.23 (d, J = 4.0 Hz, 3H) ppm. 13C NMR
(100 MHz, CDCl3) δ 262.18, 219.77, 164.52, 154.34,
142.62, 136.18, 133.86, 129.30, 128.64, 126.19, 124.29,
122.88, 122.69, 122.50, 122.15, 115.88, 115.19, 79.93,
22.89, 20.47, 20.19, 16.57 ppm. IR (KBr): 3265.32,
3147.25, 2919.04, 2733.12, 1683.54, 1579.64, 1480.09,
1450.53, 1410.92, 1261.70, 1181.84, 1109.73, 1065.07,
1032.41, 954.52, 913.69, 875.45, 847.93, 746.58, 661.37,
574.22, 498.57, 445.42 cm−1. ESI‐MS [M + H]+ calcd for
C38H44N2O2RuS: 694.2167; found: 695.2274.
4.2.6 | 2‐Isopropyl‐6‐mercaptophenol
(9b)[29]
The synthesis method is the same as that of 9a. It did not
require further purification and the product was yellow
1
oil (yield 62%). H NMR (400 MHz, CDCl3) δ 7.30 (d,
J = 7.7 Hz, 1H), 7.17 (d, J = 7.6 Hz, 1H), 6.80 (t,
J = 7.7 Hz, 1H), 6.44 (s, 1H), 3.28 (dt, J = 13.8, 6.9 Hz,
1H), 2.87 (s, 1H), 1.23 (d, J = 7.0 Hz, 6H) ppm. 13C
NMR (100 MHz, CDCl3) δ 154.11, 134.97, 133.37,
127.67, 120.47, 110.84, 27.83, 22.51 ppm.
4.2.7 | 7‐(Tert‐butyl)benzo[d][1,3]oxathiol‐
2‐one (8c)[20]
The synthesis method is the same as that of 8a and it was
purified by column chromatography to provide white
1
solid (yield 82%). H NMR (400 MHz, CDCl3) δ 7.26 (t,
J = 6.3 Hz, 2H), 7.18 (t, J = 7.7 Hz, 1H), 1.43 (s, 9H)
ppm. 13C NMR (100 MHz, CDCl3) δ 168.77, 146.08,
135.78, 124.93, 123.62, 120.12, 34.80, 29.49 ppm.
4.2.8 | 2‐(Tert‐butyl)‐6‐mercaptophenol
(9c)[29]
4.2.11 | Preparation of Ru‐based dithiolate
complex (11b)
The synthesis method is the same as that of 9a. It did not
require further purification and the product was yellow
Under N2 atmosphere, Grubbs‐Hoveyda II (250 mg,
0.40 mmol, 1 equiv.) and 10b (120 mg, 0.52 mmol, 1.3
equiv.) were added into a 2‐dram vial charged with a stir
bar, 5 ml THF was added at 0 °C. The resulting mixture
was allowed to stir at 6 °C for 1 hr, and then the solvent
was centrifuged under N2. After collecting the solution, it
1
oil (yield 56%). H NMR (400 MHz, CDCl3) δ 7.35 (d,
J = 7.4 Hz, 1H), 7.25 (d, J = 7.6 Hz, 1H), 6.76 (t,
J = 7.4 Hz, 1H), 6.56 (s, 1H), 2.80 (s, 1H), 1.39 (s, 9H)
ppm. 13C NMR (100 MHz, CDCl3) δ 155.48, 136.36,
134.14, 128.48, 119.94, 111.58, 35.06, 29.45 ppm.

8 of 10
WANG ET AL.
was drained to a solid, and the solid was washed with dry
ether (3 x 5 ml) and dried. The product was pure enough
and without further purification. Ru‐Based complex (11b)
obtained as orange‐brown solid (205 mg, 0.28 mmol, 71%
yield). The solid was dissolved with a small amount of
dichloromethane and n‐hexane was added dropwise to
the solution to saturate the solution. The saturated solu-
tion was allowed to stand at −18 °C overnight, brown
crystals precipitated. Ru‐complex 11b: 1H NMR
(400 MHz, CDCl3) δ 15.57 (s, 1H), 7.30 (t, J = 7.5 Hz,
1H), 7.20 (d, J = 7.3 Hz, 1H), 7.11 (d, J = 8.1 Hz, 1H),
7.02 (s, 2H), 6.86 (t, J = 7.1 Hz, 1H), 6.65 (d, J = 7.1 Hz,
2H), 6.59 (d, J = 7.3 Hz, 1H), 6.52 (t, J = 7.3 Hz, 1H),
6.38 (s, 1H), 5.20–5.03 (m, 1H), 3.88 (s, 4H), 3.33–3.16
(m, 1H), 2.46 (s, 6H), 2.27 (s, 9H), 1.64 (d, J = 6.2 Hz,
3H), 1.30–1.17 (m, 6H), 1.07–0.99 (m, 6H) ppm. 13C
NMR (100 MHz, CDCl3) δ 262.63, 220.49, 163.81,
154.88, 143.20, 134.62, 134.14, 129.24, 126.75, 124.72,
123.39, 123.18, 117.54, 116.59, 116.10, 80.81, 26.89,
23.82, 23.25, 21.81, 21.05 ppm. IR (KBr): 3259.98,
3149.89, 2956.12, 2918.03, 1684.57, 1579.00, 1479.30,
1417.34, 1325.77, 1263.93, 1222.36, 1186.13, 1102.30,
1029.73, 915.79, 842.97, 804.22, 742.92, 665.33, 574.57,
467.32 cm−1. ESI‐MS [M + H]+ calcd for C40H48N2O2RuS:
722.2480; found: 723.2592. CCDC: 1580839.
1684.83, 1577.97, 1479.67, 1450.68, 1409.09, 1262.58,
1107.17, 1029.93, 927.96, 848.83, 807.29, 744.37, 652.67,
575.18, 521.54, 479.39, 420.63 cm−1. ESI‐MS [M + H]+
calcd for C41H50N2O2RuS: 736.2636; found: 737.2634.
4.3 | Experimental procedure for ring
opening metathesis polymerization
(ROMP) reaction
General Procedure: Add norbornene (1 mmol) to an
oven‐dried 10 ml vial equipped with a magnetic stir bar
under N2 atmosphere. A mixture was added a solution
of Ru‐complex 11a, 11b or 11c (1.0 mol%) in CH2Cl2
(2 ml) and then was vigorously stirred for 1 hr at room
temperature to the end of the reaction. When the reaction
was completed, methanol (5 ml) was added to precipitate
the polymer. It was filtered and washed twice with meth-
1
anol (5 ml) and dried under vacuum for 10 hr. The H
NMR date were showed in the supporting information.
4.4 | Experimental procedure for
cross‐metathesis (CM) reactions
General Procedure: In an oven‐dried 10 ml vial equipped
with a magnetic stir bar were placed the alkene substrate
(0.15 mmol, 1.0 equiv) and Z‐but‐2‐ene‐1,4‐diol
(0.30 mmol, 2.0 equiv) under N2 atmosphere. The mixture
was added a solution of Ru‐complex 11b (5.0 mol%) in
tetrahydrofuran (0.5 ml) and then was vigorously stirred
for 6 hr at room temperature to the end of the reaction.
Organic solvent was removed in vacuo, and then the res-
idue was purified by silica gel column chromatography
(30% Et2O in hexanes to 50% Et2O in hexanes) to give
the desired product. (If 5% AlCl3 was added into the
system, the products were predominantly E‐selective;
without AlCl3, the products were mainly selective for Z‐
olefin products.)
4.2.12 | Preparation of Ru‐based dithiolate
complex (11c)
Under N2 atmosphere, Grubbs‐Hoveyda II (250 mg,
0.40 mmol, 1.0 equiv.) and 10c (120 mg, 0.49 mmol, 1.2
equiv.) were added into a 2‐dram vial charged with a stir
bar, 5 ml THF was added at 0 °C. The resulting mixture
was allowed to stir at 6 °C for 1 hr, and then the solvent
was centrifuged under N2. After collecting the solution, it
was drained to a solid, and the solid was washed with dry
ether (3 x 5 ml) and dried. The product was pure enough
and without further purification. Ru‐Based complex (11c)
obtained as orange‐brown solid (244 mg, 0.33 mmol, 83%
1
yield). Ru‐complex 11c: H NMR (600 MHz, CDCl3) δ
4.5 | The characterization of the olefin
matathesis products 13–22
15.63 (s, 1H), 7.29 (t, J = 7.2 Hz, 1H), 7.24–7.19 (m,
1H), 7.06 (d, J = 8.2 Hz, 1H), 7.03–6.95 (m, 2H), 6.84 (t,
J = 7.3 Hz, 1H), 6.72 (d, J = 7.4 Hz, 2H), 6.63–6.56 (m,
1H), 6.47 (t, J = 7.5 Hz, 1H), 6.30 (s, 1H), 5.18 (dt,
J = 13.2, 6.6 Hz, 1H), 3.49 (q, J = 7.0 Hz, 4H), 2.47 (s,
6H), 2.34–2.17 (m, 9H), 1.68 (d, J = 6.6 Hz, 3H), 1.34 (d,
J = 10.1 Hz, 3H), 1.26 (d, J = 6.5 Hz, 3H), 1.23 (d,
J = 3.7 Hz, 9H) ppm. 13C NMR (150 MHz, CDCl3) δ
263.15, 220.45, 164.97, 154.71, 142.62, 135.77, 135.46–
135.02, 127.98, 125.61, 123.23, 122.80, 118.86, 116.01,
115.72, 79.59, 34.48, 29.91, 23.96, 21.70, 21.05 ppm. IR
(KBr): 3249.06, 3144.86, 2952.62, 2917.37, 2733.83,
4.5.1 | (E)‐5‐(4‐Nitrophenoxy)pent‐2‐en‐1‐
ol (13)
It was purified by column chromatography to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.19
(d, J = 9.1 Hz, 2H), 6.93 (d, J = 9.2 Hz, 2H), 5.91–5.69
(m, 2H), 4.14 (d, J = 3.2 Hz, 2H), 4.09 (t, J = 6.5 Hz,
2H), 2.58 (dd, J = 11.5, 5.8 Hz, 2H), 1.52 (s, 1H). 13C
NMR (100 MHz, CDCl3) δ 163.92, 141.49, 132.20,
127.27, 125.94, 114.45, 68.05, 63.38, 31.85 ppm.

WANG ET AL.
9 of 10
4.5.2 | (E)‐2‐(7‐Hydroxyhept‐5‐en‐1‐yl)
isoindoline‐1,3‐dione (14)
4.5.6 | (E)‐12‐Hydroxydodec‐10‐en‐1‐yl
benzoate (18)
It was purified by column chromatography to provide
pale yellow oil. H NMR (400 MHz, CDCl3) δ 7.82 (dd,
This was purified by column chromatography to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.04
(d, J = 7.5 Hz, 2H), 7.55 (t, J = 7.1 Hz, 1H), 7.43
(t, J = 7.4 Hz, 2H), 5.82–5.48 (m, 2H), 4.31 (t, J = 6.5 Hz,
2H), 4.08 (d, J = 4.8 Hz, 2H), 2.03 (d, J = 6.5 Hz, 2H),
1.75 (dd, J = 13.9, 6.8 Hz, 2H), 1.42 (d, J = 6.9 Hz, 3H),
1.35 (d, J = 5.5 Hz, 4H), 1.29 (s, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ 166.73, 133.47, 132.82, 130.52,
129.54, 128.89, 128.33, 65.14, 63.83, 32.21, 29.64, 29.02,
28.72, 26.03 ppm.
1
J = 5.3, 3.1 Hz, 2H), 7.70 (dd, J = 5.3, 3.1 Hz, 2H), 5.63
(d, J = 3.2 Hz, 2H), 4.06 (d, J = 1.9 Hz, 2H), 3.67
(t, J = 7.3 Hz, 2H), 2.08 (dd, J = 10.5, 7.1 Hz, 2H), 1.67
(dt, J = 15.1, 7.5 Hz, 2H), 1.60 (s, 1H), 1.50–1.35
(m, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 168.48,
133.91, 132.38, 132.12, 129.70, 123.20, 63.71, 37.78,
31.64, 27.92, 26.14 ppm.
4.5.3 | (E)‐7‐Hydroxyhept‐5‐en‐1‐yl benzo-
ate (15)
4.5.7 | (E)‐4‐((4‐Nitrophenyl)amino)but‐2‐
en‐1‐ol (19)
This was purified by column chromatography to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.04
(d, J = 7.4 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.44
This was purified by column chromatography to provide
1
dark yellow oil. H NMR (400 MHz, CDCl3) δ 8.06 (d,
(t,
J = 7.6 Hz, 2H), 5.79–5.58 (m, 2H), 4.32
J = 9.0 Hz, 2H), 6.53 (d, J = 9.1 Hz, 2H), 6.05–
5.66 (m, 2H), 4.78 (s, 1H), 4.17 (s, 2H), 3.87 (t,
J = 5.2 Hz, 2H), 1.72 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3) δ 153.13, 138.11, 132.18, 126.41,
111.28, 62.70, 44.68 ppm.
(t, J = 6.6 Hz, 2H), 4.09 (d, J = 3.8 Hz, 2H), 2.21–2.06
(m, 2H), 1.86–1.71 (m, 2H), 1.55 (dt, J = 14.8, 7.5 Hz,
2H), 1.46 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ
166.70, 132.89, 132.52, 130.42, 129.57, 128.36, 64.85,
63.72, 31.80, 28.23, 25.51.
4.5.8 | Methyl (E)‐4‐((5‐hydroxypent‐3‐en‐
1‐yl)oxy)benzoate (20)
4.5.4 | (E)‐1‐(4‐Hydroxy‐3‐(4‐hydroxybut‐2‐
en‐1‐yl)phenyl)Ethan‐1‐one (16)
This was purified by column chromatography to provide
pale yellow oil. H NMR (400 MHz, CDCl3) δ 7.97 (d,
This was purified by column chromatography to provide
white solid. H NMR (400 MHz, MeOD‐d4) δ 7.70–7.61
1
1
J = 8.4 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 5.78 (s, 2H),
4.12 (s, 2H), 4.04 (t, J = 6.4 Hz, 2H), 3.87 (s, 3H), 2.55
(d, J = 4.3 Hz, 2H), 1.74 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3) δ 166.91, 162.63, 131.90, 131.60,
127.76, 122.57, 114.18, 67.39, 63.44, 51.89, 31.99 ppm.
(m, 2H), 6.77–6.67 (m, 1H), 5.83–5.69 (m, 1H), 5.63–5.48
(m, 1H), 3.93 (dd, J = 5.7, 0.9 Hz, 2H), 3.28 (d,
J = 6.7 Hz, 2H), 3.21 (dt, J = 3.2, 1.6 Hz, 1H), 2.41 (s,
3H), 1.22–1.16 (m, 1H) ppm. 13C NMR (100 MHz,
MeOD‐d4) δ 198.32, 160.28, 130.65, 130.25, 129.40,
128.72, 126.99, 114.11, 62.16, 32.12, 24.87 ppm.
4.5.9 | (E)‐5‐(2‐Bromophenoxy)pent‐2‐en‐
1‐ol (21)
4.5.5 | (E)‐4‐Hydroxybut‐2‐en‐1‐yl benzo-
ate (17)
This was purified by column chromatography to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.54
(d, J = 7.9 Hz, 1H), 7.26 (q, J = 7.9 Hz, 2H), 7.03
(t, J = 7.0 Hz, 1H), 5.74 (s, 2H), 4.11 (s, 2H), 2.99
(t, J = 7.2 Hz, 2H), 2.45 (s, 2H), 1.67 (s, 1H) ppm. 13C
NMR (100 MHz, CDCl3) δ 137.89, 133.04, 131.87,
131.17, 129.85, 128.08, 127.74, 126.59, 63.41, 32.47,
31.25 ppm.
This was purified by column chromatography to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.05
(d, J = 7.3 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.44
(t, J = 7.7 Hz, 2H), 6.12–5.84 (m, 2H), 4.84 (d, J = 5.5 Hz,
2H), 4.21 (d, J = 4.0 Hz, 2H), 1.70 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3) δ 166.37, 133.51, 133.07, 130.10,
129.65, 128.41, 125.15, 64.70, 62.78 ppm.

10 of 10
WANG ET AL.
[14] B. K. Keitz, K. Endo, P. R. Patel, M. B. Herbert, R. H. Grubbs,
4.5.10 | (E)‐4‐((7‐Hydroxyhept‐5‐en‐1‐yl)
J. Am. Chem. Soc. 2012, 134, 693.
oxy)benzonitrile (22)
[15] V. M. Marx, M. B. Herbert, B. K. Keitz, R. H. Grubbs, J. Am.
Chem. Soc. 2013, 135, 94.
This was purified by column chromate‐graphy to provide
pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.57
(d, J = 8.8 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 5.76–5.61
(m, 2H), 4.10 (d, J = 4.2 Hz, 2H), 4.00 (t, J = 6.4 Hz,
2H), 2.21–2.09 (m, 2H), 1.87–1.77 (m, 2H), 1.60–1.54
(m, 2H), 1.33 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3)
δ 162.37, 133.99, 132.40, 129.61, 119.30, 115.17, 103.76,
68.14, 63.69, 31.78, 28.46, 25.43 ppm.
[16] (a)R. K. M. Khan, S. Torker, A. H. Hoveyda, J. Am. Chem. Soc.
2013, 135, 10258. (b)M. J. Koh, R. K. M. Khan, S. Torker, A. H.
Hoveyda, Angew. Chem. Int. Ed. 2014, 53, 1968.
[17] (a)M. J. Koh, R. K. M. Khan, S. Torker, M. Yu, M. S. Mikus, A.
H. Hoveyda, Nature 2015, 517, 181. (b)C. Xu, X. Shen, A. H.
Hoveyda, J. Am. Chem. Soc. 2017, 139, 10919. (c)T. S. Ahmed,
R. H. Grubbs, Angew. Chem. Int. Ed. 2017, 56, 11213.
[18] M. S. Mikus, S. Torker, C. Xu, B. Li, A. H. Hoveyda, Organome-
tallics 2016, 35, 3878.
[19] C. E. Diesendruck, E. Tzur, A. Ben‐Asuly, I. Goldberg, B. F.
Straub, N. G. Lemcoff, Inorg. Chem. 2009, 48, 10819.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science
Foundation of China (grant No. 21572155 and 21372175)
and JJKH20180554KJ.
[20] Y. Zhao, Y. Xie, C. Xia, H. Huang, Adv. Synth. Catal. 2014,
356, 2471.
[21] (a)R. K. M. Khan, S. Torker, A. H. Hoveyda, J. Am. Chem. Soc.
2014, 136, 14337. (b)M. B. Herbert, Y. Lan, B. K. Keitz, P. Liu,
K. Endo, M. W. Day, K. N. Houk, R. H. Grubbs, J. Am. Chem.
Soc. 2012, 134, 7861.
ORCID
Tao Wang https://orcid.org/0000-0003-2675-7039
Jianhui Wang https://orcid.org/0000-0003-2581-7247
[22] Y. Shoji, R. Ishige, T. Higashihara, J. Watanabe, M. Ueda, Mac-
romolecules 2010, 43, 805.
[23] T. Kitagawa, J. Nishino, T. Inomata, T. Ozawa, Y. Funahashi,
H. Masuda, Chem. Commun. 2016, 52, 4780.
REFERENCES
[24] W. Yu, X. H. Xu, F. L. Qing, Adv. Synth. Catal. 2015, 357, 2039.
[1] A. H. Hoveyda, J. Org. Chem. 2014, 79, 4763.
[25] J. H. Liao, L. F. Fan, W. Guo, Z. M. Zhang, J. W. Li, C. L. Zhu,
[2] A. H. Hoveyda, R. K. M. Khan, S. Torker, S. J. Malcolmson,
Y. W. Ren, W. Q. Wu, H. F. Jiang, Org. Lett. 2017, 19, 1008.
Handbook of Metathesis, Wiley‐VCH, Weinheim 2015, 503.
[26] H. M. Dai, C. Yu, C. S. Lu, H. Yan, Eur. J. Org. Chem. 2016,
2016, 1255.
[3] S. J. Meek, R. V. O'Brien, J. Llaveria, R. R. Schrock, A. H.
Hoveyda, Nature 2011, 471, 461.
[27] L. L. Danilov, N. M. Balagurova, A. N. Vinnikova, N. S. Utkina,
V. I. Torgov, N. A. Kalinchuk, T. N. Druzhinina, V. V.
Veselovsky, Russ. J. Bioorg. Chem. 2014, 40, 89.
[4] (a)I. Ibrahem, M. Yu, R. R. Schrock, A. H. Hoveyda, J. Am.
Chem. Soc. 2013, 131, 3844. (b)M. Yu, I. Ibrahem, M. Hasegawa,
R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2012, 134, 2788.
[28] T. Claire, G. Hansjörg, D. Bernard, R. Louis, L. F. Pascal, Eur. J.
Inorg. Chem. 2006, 19, 3911.
[5] S. J. Malcolmson, S. J. Meek, E. S. Sattely, R. R. Schrock, A. H.
Hoveyda, Nature 2008, 456, 933.
[29] K. Shiori, I. Takeo, K. Miki, T. Ryuichi, T. Mikimasa, K. Tetsuo,
I. Hitoshi, M. Atsushi, S. Takuya, E. Takashi, N. Kazuhiko, T.
Koji, A. Kousuke, T. Takuya, T. Ryusuke, H. Nozomi, M.
Naoaki, O. Atsushi, K. Kaori, Y. Yusuke, K. Tatsuya, Patent
No. US 20160311858, May 27, 2016.
[6] H. Zhang, E. C. Yu, S. Torker, R. R. Schrock, A. H. Hoveyda,
J. Am. Chem. Soc. 2014, 136, 16493.
[7] M. F. Cain, W. P. Forrest, D. V. Peryshkov, R. R. Schrock, P.
Müller, J. Am. Chem. Soc. 2013, 135, 15338.
[8] M. Bornand, P. Chen, Angew. Chem. Int. Ed. 2005, 44, 7909.
[9] J. J. Van Veldhuizen, S. B. Garber, J. S. Kingsbury, A. H.
SUPPORTING INFORMATION
Hoveyda, J. Am. Chem. Soc. 2002, 124, 4954.
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
[10] J. J. Van Veldhuizen, J. E. Campbell, R. E. Giudici, A. H.
Hoveyda, J. Am. Chem. Soc. 2005, 127, 6877.
[11] K. Endo, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133, 8525.
[12] (a)A. W. H. Speed, T. J. Mann, R. V. O'Brien, R. R. Schrock, A.
H. Hoveyda, J. Am.Chem. Soc. 2014, 136, 16136. (b)M. Yu, C. B.
Wang, A. F. Kyle, P. Jakubec, D. J. Dixon, R. R. Schrock, A. H.
Hoveyda, Nature 2011, 479, 88.
How to cite this article: Wang T, Yu X, Zhang
H, Wu S, Guo W, Wang J. Synthesis and Evaluation
of Ruthenium 2‐Alkyl‐6‐mercaptophenolate
Catalysts for Olefin Metathesis. Appl Organometal
Chem. 2019;e4939. https://doi.org/10.1002/aoc.4939
[13] (a)M. J. Koh, T. T. Nguyen, J. K. Lam, S. Torker, J. Hyvl, R. R.
Schrock, A. H. Hoveyda, Nature 2017, 542, 80. (b)T. T. Nguyen,
M. J. Koh, T. J. Mann, R. R. Schrock, A. H. Hoveyda, Nature
2017, 552, 347.