A 3,4-dimercapto-3-cyclobutene-1,2-dione-chelated ruthenium carbene catalyst for: Z -stereoretentive/stereoselective olefin metathesis

Article abstract of DOI:10.1039/c9dt01016e

A ruthenium carbene catalyst chelated with a 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand was synthesized and its molecular structure was determined by single-crystal X-ray diffraction. The Ru catalyst had excellent catalytic activity with high yields and good Z/E ratios for the ring opening metathesis polymerization (ROMP) of norbornene (yield: 96%/Z/E: 86 : 14) and 1,5-cyclooctadiene (yield: 86%/Z/E: 91 : 9) and for ring opening cross metathesis (ROCM) reactions of norbornene/5-norbornene-2-exo, 3-exo-dimethanol with styrene (yields: 64%-92%/Z/E: 97 : 3-98 : 2) or 4-fluorostyrene (yield: 46%-94%/Z/E: 98 : 2). The catalyst also had high Z-stereoretentivity (91 : 9-98 : 2) for cross-metathesis (CM) reactions of terminal olefins with (Z)-2-butene-1,4-diol. More importantly, the catalyst had moderate Z-stereoselectivity for homometathesis reactions of terminal olefins giving cis-olefins as the major products (Z/E ratios of 70 : 30-77 : 23). Like other Ru carbene complexes, the catalyst tolerates many different functional groups. The presented data, supported by DFT calculations, show that our catalyst, bearing a chelating 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand, exhibits higher stability towards air than Hoveyda's stereoretentive complex systems.

Full text of DOI:10.1039/c9dt01016e

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DOI: 10.1039/C9DT01016E
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ARTICLE
3,4-Dimercapto-3-cyclobutene-1,2-dione-chelated Ruthenium
Carbene Catalyst for Z-Stereoretentive/Stereoselective Olefin
Metathesis
Received 00th January 20xx,
Accepted 00th January 20xx
Tao Wang,a, b Qingxiao Xie,a, b Weijie Guo,a, b Shutao Wu,a, b Huiqing Zhang,a, b Jianhui Wang,*, a, b
Botao Wu*, b, c, d
DOI: 10.1039/x0xx00000x
www.rsc.org/
A ruthenium carbene catalyst chelated with a 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand was synthesized and its
molecular structure was determined by single-crystal X-ray diffraction. The Ru catalyst had excellent catalytic activity with
high yields and good Z/E ratios for the ring opening metathesis polymerization (ROMP) of norbornene (yield:96%/Z/E:86:14)
and 1,5-cyclooctadiene (yield:86%/Z/E:91:9) and for ring opening cross metathesis (ROCM) reactions of norbornene/5-
norbornene-2-exo, 3-exo-dimethanol with styrene (yields:64%-92%/Z/E:97:3-98:2) or 4-fluorostyrene (yield: 46%-
94%/Z/E:98:2). The catalyst also had high Z-stereoretentivity (91:9–98:2) for cross-metathesis (CM) reactions of terminal
olefins with (Z)-2-butene-1,4-diol. More importantly, the catalyst had moderate Z-stereoselectivity for homometathesis
reactions of terminal olefins giving cis-olefins as the major products (Z/E ratios of 70:30–77:23). Like other Ru carbene
complexes, the catalyst tolerates many different functional groups. Presented data, supported with DFT calculations, show
that our catalyst, bearing
a
chelating 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand, exhibits higher
stability towards air than Hoveyda’s stereoretentive complex systems.
In 2011, Grubbs and co-workers reported a Z-selective Ru
olefin metathesis catalyst 3 (Fig. 1)[7] containing an N-
heterocyclic carbene (NHC) with a carbanion bidentate ligand.
Complex 3 can efficiently catalyze the CM of terminal olefins in
different solvents and at different temperatures with good Z-
selectivities. In addition, like other Ru carbene catalysts, 3 has
excellent functional group compatibility, which greatly
broadens the scope of applications for Z-selective olefin
metathesis reactions.[8]
Introduction
Olefin metathesis is an extremely important reaction that
builds C-C bond skeletons.[1] Commercially available Ru carbene
olefin metathesis catalysts (e.g., Grubbs I and II and Grubbs-
Hoveyda I and II catalysts) usually produce high proportions of
E-olefin products in cross-metathesis (CM), ring-opening
metathesis (ROM), and ring-closing metathesis (RCM) reactions.
Since many natural products, including oleic acid,[2a,b]
civetone,[2c] and substances with anticancer activity,[2d-f] often
contain Z-olefin frameworks. The design of metathesis catalysts
that can selectively generate Z-olefin products has been an
important and challenging pursuit[3] since the 21st century. One
of the most significant achievements was the synthesis of Mo
complex 1 which has a monopyrrole ligand (Fig. 1) in 2009 by
Ibrahem et al.[4] This complex produces a high proportion of Z-
olefin products in ring opening cross metathesis (ROCM)
reactions. The structure of 1 has been incorporated and
optimized in the design of other Mo and W complexes (Fig. 1)
to give a series of Z-selective olefin metathesis catalysts.[5]
These catalysts have been successfully applied to CM reactions
and RCM reactions to form macrocyclic compounds.[6]
The catalytic performance of these Ru complexes is
substantially affected by the carboxylic acid ligand and aryl
group on the NHC. For example, when the carboxylic acid ligand
is replaced with
a monodentate halogen ligand the
stereoselectivity of the catalyst is markedly reduced. Changing
the carboxylic acid ligand slightly affects the catalyst
stereoselectivity. When the carboxyl ligand was replaced with a
nitrate group to give complex 4 (Fig. 1), both the catalytic
activity and selectivity improved greatly (turnover number (TON)
~ 1000).[9] When complex 4 was applied to the ring opening
metathesis polymerization (ROMP) of norbornene, the ratio of
cis-polymer largely depended on the monomer structure and
the reaction temperature.[10] At low temperatures the ratios of
cis-polymers were obtained as high as 96%. In 2013, Grubbs
found that replacing the Mes- group of the NHC ligand with a
more crowded 2,6-diisopropylbenzene group resulted in a
catalyst with a higher activity and better Z-selectivity (Z-
selectivity > 95%; TON = 7400).[11] Asymmetrically modified
catalysts have been applied to the asymmetric ROM of cyclic
a. Department of Chemistry, College of Science, Tianjin University, Tianjin 300350, P.
R. China. E-mail: wjh@tju.edu.cn.
b. Collaborative Innovation center of Chemical Science and Engineering (Tianjin)
300072, P. R. China.
c. School of Chemical Engineering & Technology, Tianjin University, Tianjin 300350,
P. R. China. beautywu@tju.edu.cn.
d. College of Chemistry and Molecular Engineering, Peking University, Beijing
100871, China.
Electronic Supplementary Information (ESI) available: See
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olefins to give chiral structures containing Z-olefins (98% Z; 95% value of L3 is 4.20, which is lower than those of benzene-1,2-dithiol
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ee).[12]
(L1) and 3,6-dichlorobenzene-1,2-dithiol (L2). Therefore the use of L3
as a ligand should reduce the electron density of the Ru center and
thus improve the stability of the Ru complex. Herein, the synthesis of
a new Ru carbene complex with 3,4-dimercaptocyclobut-3-ene-1,2-
dione as a ligand is reported. The ability of this complex to catalyze
ROMP, ROCM and CM reactions was investigated and the results are
reported.
DOI: 10.1039/C9DT01016E
In 2013, Hoveyda and co-workers found that complex 5 (Fig. 1)
with a 1,2-benzenedithiolate ligand could catalyze ROCM and ROMP
reactions to provide highly selective Z-olefin products.[13] In 2015, the
addition of a benzene-1,2-dithiolate ligand with a 3,6-dichloro
substitution (Fig. 1) was found to remarkably increase the stability
and catalytic activity of the resulting Ru complex.[14] The CM
reactions of (Z)-but-2-ene-1,4-diol and terminal olefins catalyzed by
6 selectively gave Z-products (>96% Z).[14] In addition, complex 6 can
tolerate many common organic functional groups and allyl alcohol
compounds did not need protection. Furthermore, the conversion
rate and the Z-retentivity of the reaction system were greatly
improved. Grubbs and co-workers have also used complex 6 to
catalyze CM reactions of terminal olefins and cis- or trans-olefins to
produce the corresponding cis- and trans-products, indicating that 6
has good stereoretention.[15] Since, Ru complexes containing
dithiolate ligands have the advantages of simple structures, easy
syntheses, and good functional groups tolerance, Such as that they
have great application prospects for producing Z-olefins.
N
N
Mes
N
N
Mes
N
N
Mes
Mes
Cl
Mes
Mes
Br
I
Ru
O
Ru
O
Ru
O
Cl
I
Br
Ru-1
Ru-2
Ru-3
Electron density of Ru (II) center
Activity
Cl
O
SH
SH
SH
L1 pKa=5.90
SH
SH
O
SH
Cl
L2 pKa=4.40
L3 pKa=4.20
Cl
Cl
t-Bu
N
N
N
Fig. 2 Top: Correlation between electron density of Ru metal centers and their catalytic
activities; Bottom: Structure and pKa values of ligands used in this work. These pKa
values of the ligands were calculated using Advanced Chemistry Development (ACD/Labs)
Software V11.02 (1994-2019 ACD/Labs).
N
Ph
Mo
W
O
Br
O
Br
TBSO
Results and discussion
2
1
The synthesis of the 3,4-dimercapto-3-cyclobutene-1,2-dione
ligand and the corresponding Ru complex 11 are depicted in Scheme
1. First, the square acid (7) was converted to 3,4-diethoxycyclobut-3-
ene-1,2-dione (8) in 78% yield using the method reported in the
literature.[18] Next, 8 was reacted with sodium bisulfide in ethanol to
give disodium 3,4-dioxocyclobut-1-ene-1,2-dithiolate (9) in 80%
yield.[19] The zinc 3,4-dioxocyclobut-1-ene-1,2-dithiolate salt (10) was
obtained by reacting ethylenediamine with a methanol solution of 9
and zinc acetate (yield, 94%). The zinc salt 10 and Ru-1 were then
reacted in tetrahydrofuran (THF) at 22 °C for 2 h to give the Ru-based
N
N
N
NMes
X
S
Mes
Mes
H
O
L
Ru
O
Ru
O
S
O
X
5 X = H
6 X = Cl
t-Bu
4 L = -O N+
C
3 L =
Fig. 1 Catalysts used previously to selectively generate Z-products.
In addition to ligand structure, the electron density of the Ru
center also greatly influences the catalytic activity of a catalyst. For
example, Slugovc and co-workers found that the catalytic activity of
Grubbs-Hoveyda II (Ru-1, Fig. 2) was significantly reduced when
chlorine atoms were replaced by bromine or iodine atoms.[16] As the
electron density of the Ru atom increased (I > Br > Cl), the catalytic
activity gradually decreased (Fig. 2). Hoveyda have proposed that the
decomposition pathway of dithiolate catalysts involved a sulfide shift
and enrich the electron density of anionic ligand would prone to
deactivation.[14] Based on the above studies, we think that this
nucleophilic addition of a sulfur anion to the carbon atom of the
benzylidene carbene could be greatly inhibited by reducing the
electron density of the sulfur ligand. This would increase the energy
of the reaction barrier which should improve the stability of the Ru
complex. In order to verify our inference, we need a ligand with low
electronegativity and stable structure to coordinate with ruthenium.
3,4-Dimercaptocyclobut-3-ene-1,2-dione (Fig. 2, L3), as a stable
ligand, is used to coordinate with Cu[17a-d], Ni[17e-h], In[17i], Pt[17j] and
Pd[17c, j], but the coordination with Ru has not been studied. The pKa
1
complex 11 in 66% yield. The H NMR spectra of the complex has a
singlet peak at 15.36 ppm, which corresponds to the benzylidene
carbene protons. This indicates that the ligand exchange was
successful.
O
SNa
O
OEt
O
OH
EtOH
NaHS.6H2O
EtOH
O
SNa
O
OEt
O
OH
9
7
8
N
N
Mes
H
Mes
O
O
S
S
Grubbs-Hoveyda II
THF
S
Zn(OAc)2 2H2O
MeOH
Ru
Zn
O
O
S
O
10
11
Scheme
1 Synthesis of 3,4-dioxocyclobut-1-ene-1,2-dithiolate-chelated ruthenium
carbene complex 11.
A single crystal of complex 11 was grown by slow evaporation from
a CH2Cl2 solution at room temperature under N2 atmosphere. The
molecular structure of 11 was determined by single X-ray diffraction
2 | J. Name., 2012, 00, 1-3
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The calculated energy profile shows that the reaction begins with the
and is shown in Fig. 3. The arrangement of the ligands around the
metal center are similar to those in catalysts 5[13] and 6[14]. Complex
11 has a slightly deformed trigonal bipyramidal structure with an
NHC, two sulfides, an isopropoxy moiety and the benzylidene
carbene ligand seated around the Ru metal center. The bond
distances between the Ru center and the S atoms are 2.3137 (5) and
2.3785 (5) Å for Ru (1)–S (1) and Ru (1)–S (2), respectively. Both of
these are longer than those in catalyst 5 (Ru (1)–S (1), 2.2830 (6) Å
and Ru (1)–S (2), 2.2933 (6) Å) and catalyst 6 (Ru (1)–S (1), 2.2706 (10)
Å and Ru (1)–S (2), 2.2954 (9) Å). The bond angles of S (1)–Ru–S (2)
(90.635° (19)), S (1)–Ru (1)–O (1) (170.49° (4)) and S (2)–Ru (1)–O (1)
(90.68° (4)) in 11 are also larger than the corresponding angles in 5
and 6. These results indicate that the introduction of the 3,4-
dioxocyclobut-1-ene-1,2-dithiolate ligand to the catalyst slightly
changed the structure of the Ru center, which may change the
stability and catalytic activity of the complex.
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formation of intermediate 2 which occurs tDhOroI:u1g0h.10tr3a9n/Csi9tDioTn01s0t1a6tEe
TS1 via the coordination dissociation of O (alkoxy) from the Ru(II)
center. Next, intermediate 3 is produced by isomerization of
intermediate 1. A subsequent nucleophilic attack of the sulfur atom
on the carbene carbon atom to form Ru species intermediate 4 was
absorbed (relative to intermediate 2) by 3.7, 14.3 and 14.4 kcal/mol
(for L1, L2 and L3, respectively). These results show that the
nucleophilic addition is the rate-determining step. Therefore,
complex 11 would be expected to have better stability than
complexes 6 and 5, which is consistent with the experiment results.
Fig. 4 The activity of catalysts 5, 6 and 11 as a function of storage time. Reaction duration:
4 h; temperature: 55 oC; solvent: THF (0.5 mL); Ru complex 5, 6 and 11: 5 mol%; hex-5-
en-1-yl benzoate(0.13 mmol), (Z)-but-2-ene-1,4-diol(0.26 mmol); Conversions and Z/E
were determined by analysis of 1H NMR spectra of the mixtures; Yields are based on
isolated products.
Fig. 3 Perspective views of 11. Ellipsoids are drawn at 50% probability. For clarity,
the hydrogen atoms were omitted. The supporting materials provide detailed
bond lengths (Å) and angles (°).
In order to investigate the stability of complex 11, the
decomposition rate of the catalyst was monitored by sealing the
complex as a solid in a vial at room temperature without N2
protection for several days. For comparison, the same experiment
was performed on complexes 5 and 6. As catalysts decompose, their
activities change, so the stored complexes were used to catalyze the
CM reaction of hex-5-en-1-yl benzoate with (Z)-but-2-ene-1,4-diol.
The results are shown in Fig. 4. After 10 or 18 days respectively,
complexes 5 and 6 had no activity (0% yield) indicating that these
catalysts were completely deactivated by this time. In comparison,
after 18 days complex 11 still had a yield of 31% and did not totally
lose its catalytic activity until 30 days. Clearly catalyst 11 has better
stability than catalysts 5 and 6. In addition, there were no significant
changes in the stereoselectivity of the products over the course of
the experiments (the catalysts maintained high Z-stereoretentivity).
The 1H NMR spectra for the products are given in the SI.
Fig. 5 Calculated energy profiles of all intermediate and transition states’ for complexes
5, 6 and 11
Density functional theory (DFT) calculations were performed in
order to further validate the stability of complex 11. The calculated
energy profiles are shown in Fig. 5. Previously Hoveyda reported that
the decomposition of a dithiolate catalyst was caused by the
nucleophilic attack of S-ligand on the carbene carbon atom.[14] The
ruthenium center must provide enough space for the transition of
the hybrid orbitals of the carbene carbon atom from sp2 to sp3. We
found that the Ru−O (alkoxy) linkage is the weakest coordination
bond, because the oxygen atom is a hard donor atom and it has no
negative charge to a soft Ru(II) center. This initial Ru-O bond
dissociation process is supported by many studies.[9, 20] Indeed, we
Although no higher activity catalysts than complex 6 were
obtained by ligand design, we found that the stability of the catalyst
can be greatly improved by regulating ligands. This finding is related
to the properties of 3,4-dioxocyclobut-1-ene-1,2-dithiolate, which
illustrates low basicity and electron density of two S atoms involved
in the coordination process. Such
a strategy inhibits the
decomposition process of the catalyst and could produce high-
stability catalysts for olefin metathesis.
Complex 11 was used to catalyze ROMP reactions of norbornene
(12) and 1,5-cyclooctadiene (13). The ROMP reactions were carried
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products were obtained. This is due to the steric hindrance of the
out at room temperature, using dichloromethane as solvent without
N2 atmosphere. The complex 11 gives high yields and Z/E ratios which
are shown in the Table 1. With a catalyst load of 0.1 mol%, the
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hydroxymethyl.[21]
DOI: 10.1039/C9DT01016E
Complex 11 was then used to catalyze CM reactions of different
polymerization of 12 was achieved in 1 h with a total yield of 96%. terminal olefins and (Z)-but-2-ene-1,4-diol. The results are shown in
Table 3. The CM reactions were carried out using 5 mol% of 11 in
THF. Initially, 1-(but-3-en-1-yloxy)-4-nitrobenzene and (Z)-but-2-ene-
1,4-diol were used as the substrates. When the reaction was carried
out at 25 oC, a low conversion (33%) was obtained but as the
temperature was increased to 55 oC, the yield gradually increased.
from 33% to 49%. Further increasing temperature to 65 °C, did not
significantly increase the activity of the catalyst. In order to better
elucidate the temperature effect, five other substrates (1-(hex-5-en-
1-yloxy)-4-nitrobenzene, allyl benzoate, hex-5-en-1-yl benzoate, 2-
The cis-product yield was 86%. When the catalyst load was reduced
to 0.005 mol%, after 1 h of reaction, the TON was 17950 compared
to 960 for the higher catalyst load. In contrast, the polymerization
rate of 13 was much slower. It took 22 h to achieve a yield of 86%
with a Z/E ratio of 91:9. The catalytic activities of catalyst 5 for these
reactions were also investigated. The reaction of 12, gave a yield of
94% with a Z/E ratio of 97:3 (Table 1, entry 2). Whereas, for
monomer 13, a yield of 73% with a Z/E ratio of 98:2 was obtained
(Table 1, entry 5). These results are similar to those of Khan et al.[13]
Table 1 Ru-based catalyst 11 in ROMP reactionsa
(but-3-en-1-yl)isoindoline-1,3-dione
and
2-(hex-5-en-1-
yl)isoindoline-1,3-dione) were also tested and the results are shown
o
in Table 3. All the results indicate that 55 C is the optimal reaction
Ru complex
temperature. Complex 6 was also used for the CM reactions using
the optimum conditions and relatively high yields (49-85%) with Z/E
product ratios of 92:8–98:2 were obtained. This indicates that
although the stability of catalyst 11 has been greatly improved by the
introduction of the new ligand, the activity of catalyst 11 still
n
CH2Cl2, 1h, 22 o
C
12
14
Ru complex
CH2Cl2, 22h, 22 o
C
n
Table 3 Stereoretentivity and activity study of Ru-based catalyst 11 in CM reactions of
15
13
different terminal alkenes and (Z)-but-2-ene-1,4-diol.a, b,c,d
entry monomer cat. mol% time
yield/Z:Eb
TON
960
940
5 mol% cat.
THF, 55 oC, 4 h
G
HO
OH
G
OH
C
A
B
+
1
12
11
5
0.1
0.1
1 h
96%/86:14
94%/97:3
Product
con./yield Z/E
Product
con./yield Z/E
2
3
4
5
12
12
13
13
1 h
1 h
33/28% 97:3(25 oC)
97:3(35 oC)
38/33%
O
O
96:4(45 oC)
45/39%
47/40% 97:3(55 oC)
O
26
OH
OH
2
O2N
O
2
OH
11 0.005
85%/86:14 17950
96:4(55 oC)
49/45%
96:4(55 oC)
64/56%
95:5(65 oC)
50/44%
20
95:5(55 oC)
11
5
0.1
0.1
22 h
24 h
86%/91:9
73%/98:2
860
730
85/78%
36/30% 98:2(25 oC)
O
97:3(55 oC)
53/46%
98:2(35 oC)
44/39%
O
4
71/63% 97:3(55 oC)
98:2(45 oC)
50/44%
O2N
O
OH
4
O
27
58/51% 98:2(55 oC)
a Solvent: CH2Cl2 (2 mL); temperature: 22 oC; b Z/E ratios were determined from 1H NMR
97:3(65 oC)
57/52%
21
spectra of the pure products; c yields are based on pure products.
97:3(55 oC)
O
O
88/82%
18/13% 98:2(25 oC)
24/19% 98:2(35 oC)
95:5(55 oC)
66/60%
Table 2 Ru-based catalyst 11 in ROCM reactions.a,b
9
OH
97:3(55 oC)
O
92/85%
97:3(45 oC)
32/26%
O
OH
28
97:3(55 oC)
39/33%
R
11
Ru complex
THF, 22 o
42/35% 97:3(65 oC)
22
+
O
OH
2
96:4(55 oC)
57/50%
38/31%
57/52%
R
20.0 equiv.
R
96:4(55 oC)
C
95:5(55 oC)
CHO
98:2(25 oC)
40/35%
29
1.0 equiv.
substrate
O
O
98:2(35 oC)
47/42%
97:3(45 oC)
58/52%
OH
entry
1
cat.
product
yield Z/E
4
OH
96:4(55 oC)
65/57%
O
93:7(55 oC)
49/43%
81/72%
96:4(65 oC)
67/61%
97:3
78%
OH
18a
18b
R=C6H5
R=4-FC6H4
1 mol%
1 mol%
23
96:4(55 oC)
97:3(55 oC)
79/72%
62%
98:2
R
98:2(25 oC)
33/27%
30
O
12
18
37/33% 98:2(35 oC)
19a
19a
1 mol%
2 mol%
64% 98:2
98:2
92%
HO
OH
OH
F3C
N
OH
2
97:3(45 oC)
47/41%
R=C6H5
97:3(55 oC)
51/44%
35/29% 91:9(55 oC)
R
O
2
3
96:4(65 oC)
50/45%
65/59% 92:8(55 oC)
OH
1 mol%
3 mol%
19b
19b
46% 98:2
94%
R=4-FC6H4
24
97:3(55 oC)
68/62%
OH
HO
98:2
19
31
32
98:2(25oC)
97:3(35oC)
16 (exo)
36/32%
44/39%
O
HO
53/48% 97:3(45oC)
N
OH
4
29/23% 92:8(55 oC)
97:3(55oC)
59/53%
OH
1 mol%
1 mol%
non.
non.
---
---
---
---
93:7(55 oC)
54/49%
R=C6H5
R=4-FC6H4
O
97:3(65oC)
62/55%
25
98:2(55 oC)
78/71%
17 (endo)
a
Reaction duration: 4 h; solvent: THF (0.5 mL); Ru complex 11: 5 mol%; A:B = 1.0:2.0
a Solvent: THF (0.5 mL); temperature: 22 oC; time: 4 h; b Z/E ratios were determined from
equiv.; under N2 atmosphere; Conversions and Z/E ratios were determined from 1H
NMR spectra of the mixtures; Yields are based on isolated products; The catalytic
b
1H NMR spectra of the pure products; c yields are based on pure products.
c
d
results for catalyst 6 are shown in bold at the bottom of each set of data.
Next the reaction scope of complex 11 for catalyzing ROCM
reactions was investigated and the results are shown in Table 2. With needs to be improved. The data from Table 3 also demonstrates the
a catalyst load of 1.0 mol% the reactions of 12 with styrene and 4- functional group tolerance of catalyst 11. Like other Ru carbene
fluorostyrene gave good yields (78% and 62%, respectively) and good catalysts, complex 11 tolerates many common functional groups,
Z/E ratios (97:3 and 98:2, respectively) (Table 2, entry 1). However such as nitro (20 and 21), ketone (30) and aldehyde (29) groups.
with 1.0 mol% of complex 11, the reactions of 5-norbornene-2-exo, When terminal olefins with similar structures and different alkyl
3-exo-dimethanol (16) with styrene and 4-fluorostyrene gave chain lengths were used, the terminal olefins with longer chains gave
moderate yields (64%/46%) with high Z/E ratios (98:2). When the higher yields than those with shorter chains (like 22, 23 and 28).
catalyst load was increased to 2.0 and 3.0 mol%, high Z/E ratios (98:2) Furthermore, the activity of catalyst 11 did not decrease even
and high yields (92%/94%) were obtained. When 5-norbornene-2- without nitrogen protection.
endo, 3-endo-dimethanol (17) was used as the substrate, no
4 | J. Name., 2012, 00, 1-3
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Dalton Transactions
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ARTICLE
Complex 11 was then used to catalyze the homometathesis Ru carbene complex has a high functional group tolerance which is
reactions of terminal olefins and the results are shown in Table 4. similar to that of other Ru carbene olefin meDtaOthI:e10si.s10c3Va9ite/awClyA9srDtticTsl.0e1O0n1li6nEe
These reactions gave low yields with Z-olefins selectivities from 70:30
to 77:23. The CM reaction of hex-5-en-1-yl benzoate and 2-(hex-5-
en-1-yl)isoindoline-1,3-dione at a molecular ratio of 1:1.5 gave 38 in
low yield, because the homometathesis reactions also resulted in by-
Experimental Section
General Information
products 33 (5%) and 36 (9%). The homometathesis products
1H-NMR and 13C-NMR spectra were acquired in CDCl3 on a
observed in this reaction system may contribute to the low yield of
Bruker (AVANCE III ) 400 MHz spectrometer. If not otherwise
noted, chemical shift values are reported in ppm relative to
residual CDCl3 (J =7.26) for the 1H-NMR spectra and relative to
CDCl3 (77.1 ppm) for the 13C-NMR spectra. Multiplicities are
described using the following abbreviations: singlet (s), doublet
(d), doublet of doublets (dd), triplet (t), quartet (q), and
multiplet (m). The H coupling constants (J) are given in Hz.
High-resolution mass spectra were obtained on a JEOL JMS-
DX303 mass spectrometer.
the CM reactions. However, the major product 38 still possessed a
Z/E ratio of 70:30. This indicates that catalyst 11 can generate Z-
olefin products without inheriting the original configuration of the
substrates. In addition, complex 6 was used for the homometathesis
reactions under the same conditions as complex 11 and the relatively
yields (31-59%) with Z/E product ratios of 67:33–74:26 were
obtained. This indicates that the catalytic activity of catalyst 6 is
higher than those of 11, but the Z-stereoselectivity not much
difference between these two catalysts. Overall, these experiments
demonstrate that the products obtained (Table 3, 20-32) from the
CM reactions of terminal olefins with (Z)-but-2-ene-1,4-diol generally
inherit the cis-structure of (Z)-but-2-ene-1,4-diol even though
catalyst 11 is a Z-selective catalyst.
1
DFT calculations were performed using a Gaussian 09
package.[22] Geometry optimizations were performed at the
BP86-D3BJ[23, 24, 25]/LanL2dz[26] levels for Ru and at the level 6-
31G(d)[27] for other atoms. Single-point electronic energy
calculations were performed at the BP86-D3BJ/def2-TZVP[28]
levels for Ru and at the 6-311+G(2df,2p) levels for other atoms.
The computed structures were illustrated using CYL View.[29]
Table 4 Z-selective CM reactions with terminal olefins catalyzed by the Ru-based catalyst
11a, b, c, d
10 mol % cat.
THF, 55 oC, 6 h
G
G
G
Materials and Methods
entry
1
substrate
product
con./yield
Z/E
Unless otherwise noted, all reactions were performed under an
atmosphere of dry N2 with oven-dried glassware and with anhydrous
solvents using standard dry box or vacuum line techniques. Toluene,
THF, hexane and Et2O was distilled from sodium/benzophenone
under a N2 atmosphere. Ethanol was distilled over MgSO4. CH2Cl2 was
dried over CaH2, and distilled prior to use. All other solvents were
dried over 4-8 Å mesh molecular sieves (Aldrich) and were either
saturated with dry argon or degassed before use. Reactions were
monitored by analytical thin layer chromatography (TLC) using 0.20
mm Yantai Huagong silica gel plates. Silica gel (200-300 mesh) (from
Yantai Huagong Company) was used for flash chromatography. CDCl3
and CD2Cl2 were purchased from TCI (Shanghai) Development Co.,
Ltd. and used as received. All other chemicals or reagents were
obtained from commercial sources.
O
O
O
N
O
42/38%
55/48%
70:30
65:35
4
N
4N
4
O
O
33
O
O2N
4
2
3
NO2
40/37%
48/42%
74:26
74:26
O
4 O
O2N
4
34
O
O
O
O
O
O
O
4O
46/42%
58/53%
71:29
67:33
O
4
4
35
O
O
O
O
O
4
5
53/47%
64/59%
75:25
72:28
4 O
4
4
36
O
O
O
4
4
4
38/34%
77:23
47/41%
71:29
O2N
NO2
NO2
37
O
N
O
4
O
N
O
O
Experimental details
6
1.5 equiv.
30/27%
36/31%
70:30
67:33
4 O
4
3,4-diethoxycyclobut-3-ene-1,2-dione (8): 1H NMR (400 MHz,
CDCl3) δ 4.72 (dq, J = 14.3, 7.2 Hz, 4H), 1.60 –1.35 (m, 6H) ppm;
13C{1H} (100 MHz, CDCl3) δ 189.2, 184.1, 70.5, 15.5 ppm.
+
O
1.0 equiv.
38
O
4
a Reaction duration: 6 h; Solvent: THF (0.5 mL); Temperature: 55 oC; Ru complex: 10 mol%;
3,4-dimercapto-3-cyclobutene-1,2-dione disodium salt (9): IR
(KBr): ν 3523, 3380, 2648, 2441, 2308,1883, 1713, 1624, 1429, 1356,
1215, 1123, 1007, 923, 673, 562, 471 cm-1.
b
Conversions and Z/E ratios were determined by analysis of 1H NMR spectra of the
mixtures; c Yields are based on isolated products. d The catalytic results for catalyst 6 are
shown in bold at the bottom of each set of data.
For the preparation of 3,4-dimercapto-3-cyclobutene-1,2-dione
zinc salt (10), first 1,2-dithiosquaric acid disodium salt (1 g, 5.3 mmol,
1.0 equiv.) was added to a 100 mL single port round bottom flask
equipped with a magnetic stirrer. Next, Zn(OAc)2•2H2O (4.03 g, 18.5
mmol, 3.5 equiv.) and 50 mL of methanol were added and the
Conclusions
In summary,
a new Ru carbene complex bearing a 3,4-
dioxocyclobut-1-ene-1,2-dithiolate ligand with high Z-stereo-
retentivity/stereoselectivity was synthesized. This new Ru carbene
complex has a better stability than Hoveyda’s stereoretentive
complex systems, and excellent catalytic activities with high yields
and good Z/E ratios for ROMP/ROCM reactions without the need for
N2 protection. The Ru carbene complex also has good Z-
stereoretentivity for the reaction of terminal alkenes with (Z)-but-2-
ene-1,4-diol. For the homometathesis and CM reactions of terminal
olefins, cis-olefins products were the major products. Moreover, this
mixture was stirred at room temperature under
a nitrogen
atmosphere until the solid completely dissolved. Then
ethylenediamine solution (1.8 mL, 6.0 equiv) was added to the
reaction solution and a white solid gradually precipitated from the
solution. After stirring for 30 min, the reaction solution was filtered
and the collected solid was washed with methanol three times (10
mL x 3). The solid was then dried in a vacuum at 100 °C to give 0.93
g of the white powder 10 with a yield of 94.2%. The product was then
directly reacted without further purification. IR (KBr): ν: 3443, 3336,
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
3277, 2957, 1879, 1727, 1670, 1565, 1456, 1391, 1360, 1195, 1114, (400 MHz, CDCl3) δ 7.42 – 7.13 (m, 5H), 6.36 (d, J = 11.5 Hz, 1H), 5.82
View Article Online
1033, 940, 895, 851, 748, 663, 607, 521, 468 cm-1.
(ddd, J = 17.4, 10.2, 7.4 Hz, 1H), 5.58 (dd, J =D1O1I.:41,01.100.139H/Cz,91DHT0),1051.067E
– 4.82 (m, 2H), 3.14 – 2.96 (m, 1H), 2.64 – 2.44 (m, 1H), 2.10 – 1.96
(m, 1H), 1.96 – 1.76 (m, 2H), 1.54 – 1.44 (m, 2H), 1.28 – 1.18 (m, 1H).
13C NMR (100 MHz, CDCl3) δ 143.1, 137.9, 128.6, 128.2, 127.6, 126.51,
112.6, 44.6, 41.5, 38.7, 33.0, 31.9.
For the preparation of Ru-Based dithiolate complex (11), first zinc
1,2-dithiosquaric acid (0.51 g, 2.4 mmol, 1.0 equiv.) and Grubbs-
Hoveyda second-generation catalyst (1.5 g, 2.4 mmol, 1.0 equiv.)
were added under N2 atmosphere to a 25 mL round bottom flask
equipped with a magnetic stirrer. Next 15 mL of dry THF was added
For
(Z)-1-fluoro-4-(2-((1S,3R)3-vinylcyclopentyl)vinyl)benzene
and the reaction was stirred for 2 h at room temperature. After the (18b), complex 11 (1.0 mol%) dissolved in 0.2 mL THF was used. The
reaction was complete, the solution turned from dark green to product was purified by column chromatography with hexane to give
brown and then a yellow precipitate formed. The solution was a colorless oil (21.3 mg, yield 62%) with a Z/E ratio of 98:2. 1H NMR
filtered to give a yellow brown solid. The solid was washed with dried (400 MHz, CDCl3) δ 7.31 – 7.15 (m, 2H), 7.08 – 6.93 (m, 2H), 6.31 (d,
THF (10 mL x 3) and dried to give complex 11 as a yellow-brown solid, J = 11.5 Hz, 1H), 5.82 (ddd, J = 17.4, 10.2, 7.4 Hz, 1H), 5.56 (dd, J =
1.21 g, yield 72%. 1H NMR (400 MHz, CD2Cl2) δ 15.36 (s, 1H), 7.37 (t, 11.3, 10.1 Hz, 1H), 4.94 (dddd, J = 34.0, 10.2, 1.9, 1.1 Hz, 2H), 3.08 –
J = 7.8 Hz, 1H), 7.13 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 18.7 Hz, 2H), 6.86 2.91 (m, 1H), 2.65 – 2.45 (m, 1H), 2.01 (dt, J = 13.1, 4.4 Hz, 1H), 1.93
(dd, J = 14.2, 6.3 Hz, 2H), 6.69 (d, J = 7.3 Hz, 1H), 6.08 (s, 1H), 5.20 – – 1.78 (m, 2H), 1.54 – 1.44 (m, 2H), 1.22 (dt, J = 12.4, 10.4 Hz, 1H). 13
C
5.11 (m, 1H), 4.11 – 3.82 (m, 4H), 2.53 (s, 3H), 2.37 (s, 3H), 2.26 (s, NMR (100 MHz, CDCl3) δ 162.7, 160.3, 142.9, 137.8, 133.8, 130.1,
3H), 2.19 (s, 3H), 1.74 (d, J = 6.5 Hz, 3H), 1.56 (s, 6H), 1.41 (d, J = 6.4 126.5, 115.1, 114.9, 112.6, 44.5, 41.4, 38.6, 33.0, 31.9.
Hz, 3H).ppm. 13C{1H} NMR (100 MHz, CD2Cl2): δ 223.7, 213.5, 206.9,
189.8, 154.3, 141.7, 138.8, 135.7, 129.2, 127.9, 124.3, 122.6, 120.3,
116.0, 114.2, 112.9, 112.4, 110.0, 84.1, 75.3, 75.1, 71.2, 67.8, 31.0,
25.9, 25.6, 24.2, 21.7, 21.6, 20.9, 20.8, 20.7 ppm. IR (KBr): ν 3463,
For 3-((Z)-styryl)-5-vinylcyclopentane-1,2-diyl)dimethanol (19a),
complex 11 (1.0 mol%) dissolved in 0.2 mL THF was used. The product
was purified by column chromatography with hexane/ether (3/7) to
1
give a colorless oil (16.0 mg, yield 64%) with a Z/E ratio of 98:2. H
3335, 3275, 2973, 2924, 1810, 1736, 1707, 1581, 1479, 1427, 1368,
NMR (400 MHz, CDCl3) δ 7.37 – 7.27 (m, 2H), 7.23 (dt, J = 6.9, 5.6 Hz,
3H), 6.48 (d, J = 11.5 Hz, 1H), 5.74 (ddd, J = 17.7, 10.1, 7.8 Hz, 1H),
5.52 (dd, J = 11.4, 10.2 Hz, 1H), 5.08 – 4.92 (m, 2H), 3.58 (ddd, J =
16.9, 13.4, 8.2 Hz, 4H), 3.41 (s, 2H), 2.82 – 2.63 (m, 1H), 2.18 (dd, J =
1264, 1162, 1114, 1064, 1034, 945, 905, 871, 854, 823, 750, 715, 625,
572, 527, 420 cm-1. ESI-MS [M+Na]+calcd for C35H38N2O3Ru1S2:
700.1367; found: 723.1257. CCDC number: 1585252.
ROMP Reactions
13.7, 5.9 Hz, 1H), 2.15 – 2.07 (m, 2H), 2.01 (td, J = 12.0, 5.9 Hz, 1H),
1.36 (dd, J = 23.3, 11.3 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 141.4,
137.4, 135.8, 129.8, 128.4, 126.7, 114.5, 61.9, 50.4, 48.5, 46.3, 40.1,
39.7.
An oven-dried 10 mL vial equipped with a magnetic stir bar was
charged with 0.1 mL CH2Cl2 solution containing complex 11 (0.7 mg,
0.001 mmol). Then a solution of norbornene (94.1 mg, 1.0 mmol) in
1.5 mL CH2Cl2 was added and the solution was stirred for 1 h at room
For 3-((Z)-4-fluorostyryl)-5-vinylcyclopentane-1,2-diyl)dimethanol
temperature. The solution became very viscous. Next MeOH (5 mL) (19b), complex 11 (1.0 mol%) dissolved in 0.2 mL THF was used. The
was added and the white poly-norbornene settled out of the solution product was purified by column chromatography with hexane/ether
with vigorous stirring. The polymer was washed with MeOH (4 mL x (3/7) to give a colorless oil (12.4 mg, yield 46%) with a Z/E ratio of
3) and dried under vacuum for 24 h to give a white solid 14 (90.0 mg, 98:2. 1H NMR (400 MHz, CDCl3) δ 7.23 – 7.12 (m, 2H), 7.06 – 6.93 (m,
yield 96%) with a Z/E ratio of 86:14. 1H NMR (400 MHz, CDCl3) δ 5.22 2H), 6.42 (d, J = 11.5 Hz, 1H), 5.74 (ddd, J = 17.7, 10.1, 7.9 Hz, 1H),
(d, J = 5.9 Hz, 2H), 2.79 (s, 2H), 2.00 – 1.85 (m, 1H), 1.82 (d, J = 13.3 5.58 – 5.43 (m, 1H), 5.06 – 4.93 (m, 2H), 3.72 – 3.52 (m, 4H), 3.42 (d,
Hz, 2H), 1.36 (s, 2H), 1.02 (dd, J = 22.2, 10.7 Hz, 1H). 13C NMR (100 J = 74.1 Hz, 2H), 2.76 – 2.60 (m, 1H), 2.28 – 2.15 (m, 1H), 2.15 – 2.05
MHz, CDCl3) δ 133.9, 42.7, 38.6, 33.2.
(m, 2H), 1.97 (dt, J = 12.4, 6.1 Hz, 1H), 1.35 (dd, J = 23.3, 11.2 Hz, 1H).
13C NMR (100 MHz, CDCl3) δ 141.3, 135.8, 133.4, 130.0, 128.7, 115.3,
115.1, 114.6, 61.9, 50.4, 48.4, 46.3, 40.0, 39.7.
An oven-dried 10 mL vial equipped with a magnetic stir bar was
charged with 0.1 mL CH2Cl2 solution containing complex 11 (0.7 mg,
0.001 mmol). Then 1, 5-cyclooctadiene (108.1 mg, 1.0 mmol) was Z-Stereoretentive/Stereoselective CM Reactions.
added and the solution was stirred for 22 hours at room temperature.
General Procedure: An oven-dried 10 mL vial equipped with a
Next MeOH (5 mL) was added and the formed polymer settled out of
the solution with vigorous stirring. The polymer was washed with
MeOH (4 mL x 3) and dried under vacuum for 22 h to give 15 (93.0
mg, yield 86%) with a Z/E ratio of 91:9. 1H NMR (400 MHz, CDCl3) δ
5.39 (d, J = 4.1 Hz, 4H), 2.09 (s, 8H). 13C NMR (100 MHz, CDCl3) δ 129.6,
27.4.
magnetic stir bar was charged with the alkene substrate (0.12 mmol,
1.0 equiv.) and Z-2-butene-1,4-diol (0.24 mmol, 2.0 equiv.). To this
vessel, a solution of complex 11 or 6 (4.9 mg, 5.0 mol%) in THF (0.5
mL) was added. The resulting solution was stirred for 4-6 h at 55 oC.
The reaction media was then concentrated by vacuum. Purification
was performed using silica gel chromatography and the percent
conversion was determined using 1H NMR analysis.
ROCM Reactions
General Procedure: An oven-dried 10 mL vial equipped with a
For homometathesis reactions, an oven-dried 10 mL vial equipped
magnetic stir bar was charged with the alkene substrate (1.0 equiv.) with a magnetic stir bar was charged with alkene substrate (0.12
and a terminal olefin (20 equiv.) in a fume hood. To this vessel, a mmol, 1.0 equiv.). To this vessel, a solution of complex 11 or 6 (9.8
solution of complex 11 (1.0-3.0 mol%) in THF was added. The mg, 10.0 mol%) in THF (0.5 mL) was added. The resulting solution is
o
resulting solution was then stirred for 4 h at room temperature. The allowed was stirred for 4-6 hours at 55 C. The reaction media was
reaction mixture was then concentrated by vacuum and the product then concentrated by vacuum. Purification was performed using
was purified using silica gel chromatography.
For ((Z)-2-((1S,3R)-3-vinylcyclopentyl)vinyl)benzene
complex 11 (1.0 mol%) dissolved in 0.2 mL THF was used. The product
silica gel chromatography and the percent conversion was
determined using 1H NMR analysis.
(18a),
For (Z)-5-(4-nitrophenoxy)pent-2-en-1-ol (20)[14], complex 11 (4.9
was purified by column chromatography with hexane to give a mg, 5.0 mol%) was used. The product was purified by column
1
colorless oil (24.6 mg, yield 78%) with a Z/E ratio of 97:3. H NMR chromatography to provide a pale yellow oil (12.0 mg, yield 45%)
6 | J. Name., 2012, 00, 1-3
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1
with a Z/E ratio of 97:3. H NMR (400 MHz, CDCl3) δ 8.25–8.07 (m,
For benzoic acid, 4-[[(5Z)-7-hydroxy-5-hepten-1-yl]oxy]-, methyl
View Article Online
1H), 6.99–6.87 (m, 1H), 5.88–5.75 (m, 1H), 5.73 – 5.53 (m, 1H), 4.25 ester (27), complex 11 (4.9 mg, 5.0 mol%) waDs OusI:e1d0..1T0h3e9/pCr9oDdTu0c1t0w16aEs
(d, J = 6.7 Hz, 1H), 4.08 (t, J = 6.4 Hz, 1H), 2.63 (q, J = 6.7 Hz, 1H), 1.60 a pale yellow oil (14.6 mg, yield 46%) with a Z/E ratio of 97:3. 1H NMR
(s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ 163.7, 131.7, 127.5, 125.9, (400 MHz, CDCl3) δ 8.00–7.93 (m, 1H), 6.90 (s, 1H), 5.66 (d, J = 3.1 Hz,
114.4, 67.9, 58.5, 27.4 ppm.
1H), 5.58–5.48 (m, 1H), 4.20 (t, J = 4.9 Hz, 1H), 4.0 –3.96 (m, 1H), 3.87
(d, J = 1.9 Hz, 1H), 2.20–2.10 (m, 1H), 1.83 (d, J = 6.2 Hz, 1H), 1.64 (d,
J = 9.3 Hz, 1H), 1.60–1.49 (m, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3)
δ 166.9, 162.8, 132.3, 131.6, 129.0, 122.4, 114.0, 67.9, 58.5, 51.9,
28.6, 27.1, 26.0 ppm. ESI-MS[M+Na]+calcd for C15H20NO4: 264.3210;
found: 287.1292. Analytical Data. Found (calcd) for: C15H20NO4 C,
68.16 (68.12); H, 7.63 (6.68).
For (Z)-7-(4-nitrophenoxy)hept-2-en-1-ol (21), complex 11 (4.9 mg,
5.0 mol%) was used. The product was a pale yellow oil (15.4 mg, yield
51%) with a Z/E ratio of 98:2. 1H NMR (400 MHz, CDCl3) δ 8.21–8.12
(m, 2H), 6.97–6.88 (m, 2H), 5.67–5.59 (m, 1H), 5.58–5.48 (m, 1H),
4.19 (d, J = 6.4 Hz, 2H), 4.04 (t, J = 6.4 Hz, 2H), 2.16 (q, J = 7.4 Hz, 2H),
1.82 (dd, J = 8.5, 6.9 Hz, 2H), 1.55 (dq, J = 15.0, 7.6 Hz, 3H) ppm.
13C{1H} NMR (100 MHz, CDCl3) δ 164.1, 141.3, 132.2, 129.1, 125.9,
For (Z)-12-hydroxydodec-10-en-1-yl benzoate (28)[14], complex 11
114.4, 68.6, 58.5, 28.5, 27.0, 25.9 ppm. ESI-MS [M+Na]+ calcd for (4.9 mg, 5.0 mol%) was used. The product was a pale yellow oil (21.9
C13H17NO4: 251.2820, found: 274.1042. Analytical Data. Found mg, yield 60%) with a Z/E ratio of 95:5. 1H NMR (400 MHz, CDCl3) δ
(calcd) for: C13H17NO4 C, 62.14 (62.27); H, 6.82 (6.88); N, 5.57(5.50).
8.04 (d, J = 7.8 Hz, 1H), 7.54 (t, J = 7.3 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H),
5.65–5.55 (m, 1H), 5.55–5.43 (m, 1H), 4.30 (t, J = 6.6 Hz, 1H), 4.18 (t,
J = 5.1 Hz, 1H), 2.05 (dd, J = 13.7, 6.8 Hz, 1H), 1.80–1.71 (m, 1H), 1.53
(s, 1H), 1.48–1.39 (m, 1H), 1.34 (s, 2H), 1.28 (s, 3H) ppm. 13C{1H} NMR
(100 MHz, CDCl3) δ 133.2, 132.8, 130.5, 129.5, 128.3, 65.1, 58.6, 29.6,
29.5 – 29.2, 29.2, 28.7, 27.4, 26.0 ppm.
For (Z)-4-hydroxybut-2-en-1-yl benzoate (22)[14], complex 11 (4.9
mg, 5.0 mol%) was used. The product was a pale yellow oil (7.6 mg,
yield 33%) with a Z/E ratio of 97:3. 1H NMR (400 MHz, CDCl3) δ 8.04
(d, J = 7.7 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.7 Hz, 1H), 5.92
(dt, J = 13.0, 7.7 Hz, 1H), 5.82–5.60 (m, 1H), 4.93 (d, J = 7.0 Hz, 1H),
4.34 (d, J = 6.5 Hz, 1H), 2.13 (s, 1H) ppm. 13C{1H} NMR (100 MHz,
For
(Z)-2-((5-hydroxypent-3-en-1-yl)oxy)benzaldehyde(29),
CDCl3) δ 166.7, 133.6, 133.1, 130.0, 129.6, 128.4, 125.6, 60.6, 58.5 complex 11 (4.9 mg, 5.0 mol%) was used. The product was a pale
ppm.
yellow oil (7.7 mg, yield 31%) with a Z/E ratio of 96:4. 1H NMR (400
MHz, CDCl3) δ 10.44 (s, 1H), 7.82 (dd, J = 7.7, 1.7 Hz, 1H), 7.57 – 7.49
(m, 1H), 7.03 (t, J = 7.5 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 5.80 (dt, J =
13.2, 6.7 Hz, 1H), 5.65 (dt, J = 10.9, 7.5 Hz, 1H), 4.26 (d, J = 6.6 Hz,
2H), 4.11 (t, J = 6.4 Hz, 2H), 2.66 (q, J = 6.7 Hz, 2H), 1.66 (s, 1H) ppm.
13C{1H} NMR (100 MHz, CDCl3) δ 189.9, 161.0, 135.9, 131.5, 129.0,
127.7, 120.8, 112.6, 67.7, 58.5, 27.5 ppm. ESI-MS [M+Na]+ calcd for
C12H14O3: 206.2410, found: 229.0835. Analytical Data. Found (calcd)
for: C12H14O3 C, 69.89 (69.96); H, 6.84 (6.87).
For (Z)-7-hydroxyhept-5-en-1-yl benzoate (23)[14], complex 11 (4.9
mg, 5.0 mol%) was used. The product was a pale yellow oil (15.9 mg,
yield 57%) with a Z/E ratio of 96:4. 1H NMR (400 MHz, CDCl3) δ 8.04
(d, J = 7.7 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.7 Hz, 1H), 5.68–
5.60 (m, 1H), 5.59 –5.50 (m, 1H), 4.33 (t, J = 6.6 Hz, 1H), 4.21 (d, J =
6.6 Hz, 1H), 2.16 (q, J = 7.3 Hz, 1H), 1.81–1.75 (m, 1H), 1.67 (s, 1H),
1.54 (dt, J = 15.0, 7.5 Hz, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ
166.7, 132.9, 132.3, 130.3, 129.5, 129.0, 128.4, 64.7, 58.5, 28.2, 26.9,
25.9 ppm.
For (Z)-1-(3-hydroxy-4-(4-hydroxybut-2-en-1-yl)phenyl)e-than-1-
one (30)[14], complex 11 (4.9 mg, 5.0 mol%) was used. The product
For (Z)-2-(5-hydroxypent-3-en-1-yl)isoindoline-1,3-dione (24),
complex 11 (4.9 mg, 5.0 mol%) was used. The product was a white
solid (12.2 mg, yield 44%) with a Z/E ratio of 97:3. 1H NMR (400 MHz,
CDCl3) δ 7.84–7.76 (m, 2H), 7.72–7.64 (m, 2H), 5.73–5.62 (m, 1H),
5.56–5.45 (m, 1H), 4.11 (d, J = 6.2 Hz, 2H), 3.72 (t, J = 7.1 Hz, 2H), 2.47
(q, J = 7.3 Hz, 2H), 1.95 (s, 1H). ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
168.4, 134.0, 132.0, 131.7, 127.90, 123.2, 58.3, 37.5, 26.5 ppm. ESI-
MS[M+Na]+ calcd for C13H13NO3: 231.2510; found: 254.0744.
Analytical Data. Found (calcd) for: C13H13NO3 C, 67.52 (67.46); H, 5.67
(5.75); N, 6.06 (6.00).
1
was a white solid (10.6 mg, yield 43%) with a Z/E ratio of 93:7. H
NMR (400 MHz, CDCl3) δ 7.79 (d, J = 2.0 Hz, 1H), 7.74 (dd, J = 8.4, 2.1
Hz, 1H), 6.84 (d, J = 8.4 Hz, 1H), 5.77 (dd, J = 11.6, 5.5 Hz, 1H), 5.67
(dd, J = 18.6, 8.0 Hz, 1H), 4.36 (d, J = 6.5 Hz, 1H), 3.52 (d, J = 7.9 Hz,
1H), 2.54 (d, J = 6.8 Hz, 1H), 1.36–1.19 (m, 1H) ppm. 13C{1H} NMR (100
MHz, CDCl3) δ 197.7, 159.9, 131.8, 131.2, 129.7, 129.4, 127.6, 125.9,
115.8, 58.4, 29.7, 26.3 ppm.
For
(Z)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-ol(31)[14]
,
complex 11 (4.9 mg, 5.0 mol%) was used. The product was a pale
yellow oil (7.0 mg, yield 29%) with a Z/E ratio of 91:9. 1H NMR (400
MHz, CDCl3) δ 7.60 (d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 6.60 (d,
J = 11.8 Hz, 1H), 6.05–5.94 (m, 1H), 4.42 (d, J = 6.4 Hz, 2H), 1.66 (s,
1H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 140.1, 133.2, 129.8, 129.0,
125.2, 59.5 ppm.
For (Z)-2-(7-hydroxyhept-5-en-1-yl)isoindoline-1,3-dione (25)[14]
,
complex 11 (4.9 mg, 5.0 mol%) was used. The product was a pale
yellow oil (16.5 mg, yield 53%) with a Z/E ratio of 97:3. 1H NMR (400
MHz, CDCl3) δ 7.84 (dd, J = 5.4, 3.1 Hz, 2H), 7.72 (dd, J = 5.4, 3.0 Hz,
2H), 5.69–5.60 (m, 1H), 5.54–5.44 (m, 1H), 4.21 (d, J = 6.8 Hz, 2H),
3.73 –3.64 (m, 2H), 2.16 (q, J = 7.2 Hz, 2H), 1.76 (s, 1H), 1.72 –1.65
For (Z)-3-phenylprop-2-en-1-ol (32)[14], complex 11 (4.9 mg, 5.0
(m, 2H), 1.49–1.40 (m, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ mol%) was used. The product was a pale yellow oil (3.7 mg, yield
168.5, 133.9, 132.1, 129.2, 123.2, 58.5, 37.6, 27.7, 26.5, 26.4 ppm.
23%) with a Z/E ratio of 92:8. 1H NMR (400 MHz, CDCl3) δ 7.35 (t, J =
7.6 Hz, 2H), 7.29–7.26 (m, 1H), 7.21 (d, J = 7.6 Hz, 2H), 6.58 (d, J =
11.7 Hz, 1H), 5.88 (dt, J = 12.5, 6.4 Hz, 1H), 4.45 (d, J = 6.4 Hz, 2H),
1.55 (s, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 136.5, 131.1, 128.8,
128.3, 127.3, 59.7 ppm.
For benzoic acid, 4-[[(3Z)-5-hydroxy-3-penten-1-yl]oxy]-, methyl
ester (26), complex 11 (4.9 mg, 5.0 mol%) was used. The product was
a pale yellow oil (11.3 mg, yield 40%) with a Z/E ratio of 97:3. 1H NMR
(400 MHz, CDCl3) δ 8.02 – 7.89 (m, 2H), 6.94 – 6.81 (m, 2H), 5.84–
5.70 (m, 1H), 5.62 (dtt, J = 10.2, 7.5, 1.2 Hz, 1H), 4.22 (d, J = 6.6 Hz,
For (Z)-2,2'-(dec-5-ene-1,10-diyl)bis(isoindoline-1,3-dione) (33),
2H), 4.01 (t, J = 6.5 Hz, 2H), 3.86 (s, 3H), 2.66–2.50 (m, 2H), 1.99 (s, complex 11 (9.8 mg, 10.0 mol%) was used. The product was a pale
1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 166.8, 162.4, 131.6, 131.5, yellow solid (9.8 mg, yield 38%) with a Z/E ratio of 70:30. H NMR
1
127.9, 122.8, 114.0, 67.2, 58.4, 51.9, 27.5 ppm. ESI-MS[M+Na]+calcd (400 MHz, CDCl3) δ 7.82 (dd, J = 5.4, 3.1 Hz, 4H), 7.69 (dd, J = 5.4, 3.0
for C13H16O4: 236.2670; found: 259.0933. Analytical Data. Found Hz, 4H), 5.32 (t, J = 4.6 Hz, 2H), 3.67 (dd, J = 8.5, 6.0 Hz, 4H), 2.06 (dd,
(calcd) for: C13H16O4 C, 66.09 (66.02); H, 6.83 (6.72).
J = 12.6, 7.1 Hz, 4H), 1.67 (dd, J = 15.1, 7.5 Hz, 4H), 1.38 (dt, J = 15.0,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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7.5 Hz, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 168.4, 133.8, 132.2,
130.2, 129.6, 123.1, 37.9, 32.0, 28.1, 26.8 ppm. ESI-MS [M+Na]+ calcd
for C26H26N2O4: 430.5040, found: 453.1781. Analytical Data. Found
(calcd) for: C26H26N2O4 C, 72.54 (72.66); H, 6.09 (6.13); N, 6.51 (6.44).
Conflicts of interest
There are no conflicts to declare.
View Article Online
DOI: 10.1039/C9DT01016E
For (Z)-1,10-bis(4-nitrophenoxy)dec-5-ene (34), complex 11 (9.8
mg, 10.0 mol%) was used. The product was a white solid (9.1 mg,
yield 37%) with a Z/E ratio of 74:26. 1H NMR (400 MHz, CDCl3) δ 8.23–
8.15 (m, 4H), 7.01–6.89 (m, 4H), 5.42 (t, J = 4.6 Hz, 2H), 4.05 (t, J = 6.4
Hz, 4H), 2.13 (dd, J = 12.8, 7.3 Hz, 4H), 1.90–1.76 (m, 4H), 1.55 (dd, J
= 6.7, 3.9 Hz, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 164.1, 141.4,
130.3, 129.8, 125.9, 114.4, 68.7, 32.1, 28.5, 26.9, 25.9 ppm. ESI-
MS[M+Na]+ calcd for C22H26N2O6: 414.4580; found: 437.1720.
Analytical Data. Found (calcd) for: C22H26N2O6 C, 63.76 (63.68); H,
6.32 (6.24); N, 6.76 (6.70).
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grant No. 21572155 and 21372175), the
Natural Science Foundation of Tianjin (16JCYBJC19700).
References
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For dimethyl 4,4'-(dec-5-ene-1,10-diylbis(oxy))(Z)-dibenzo-ate
(35), complex 11 (9.8 mg, 10.0 mol%) was used. The product was a
1
pale yellow solid (11.1 mg, yield 42%) with a Z/E ratio of 71:29. H
NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.6 Hz, 4H), 6.89 (d, J = 8.7 Hz,
4H), 5.42 (dd, J = 11.0, 6.4 Hz, 2H), 4.00 (t, J = 6.4 Hz, 4H), 3.88 (s, 6H),
2.12 (dd, J = 12.8, 7.0 Hz, 4H), 1.88–1.72 (m, 4H), 1.59–1.47 (m, 4H)
ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 166.9, 162.9, 131.6, 129.8,
114.0, 68.0, 51.8, 28.7, 26.9, 26.0 ppm. ESI-MS[M+Na]+ calcd for
C26H32O6: 440.5360; found: 463.2089. Analytical Data. Found (calcd)
for: C26H32O6 C, 70.89 (70.81); H, 7.32 (7.24).
For (Z)-dec-5-ene-1,10-diyl dibenzoate (36), complex 11 (9.8 mg,
10.0 mol%) was used. The product was a pale yellow oil (10.7 mg,
yield 47%) with a Z/E ratio of 75:25. 1H NMR (400 MHz, CDCl3) δ 8.04
(d, J = 7.7 Hz, 4H), 7.55 (t, J = 7.4 Hz, 2H), 7.43 (t, J = 7.6 Hz, 4H), 5.56–
5.31 (m, 2H), 4.32 (t, J = 6.5 Hz, 4H), 2.12 (dd, J = 12.8, 7.1 Hz, 4H),
1.78 (dd, J = 10.4, 4.7 Hz, 4H), 1.61–1.41 (m, 4H) ppm. 13C{1H} NMR
(100 MHz, CDCl3) δ 166.7, 132.8, 130.4, 129.8, 129.5, 128.3, 64.9,
32.1, 28.4, 28.2, 26.8, 26.1, 26.0 ppm. ESI-MS [M+Na]+ calcd for
C24H28O4: 380.4840, found: 403.1882. Analytical Data. Found (calcd)
for: C24H28O4 C, 75.76 (75.71); H, 7.42 (7.39).
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For (Z)-1,10-bis(2-nitrophenoxy)dec-5-ene (37), complex 11 (9.8
mg, 10.0 mol%) was used. The product was a white solid (8.5 mg,
yield 34%) with a Z/E ratio of 77:23. 1H NMR (400 MHz, CDCl3) δ 7.80
(dd, J = 8.1, 1.7 Hz, 2H), 7.50 (ddd, J = 8.5, 7.5, 1.7 Hz, 2H), 7.07 (d, J
= 8.5 Hz, 2H), 7.04–6.91 (m, 2H), 5.40 (t, J = 4.6 Hz, 2H), 4.10 (dd, J =
7.5, 5.2 Hz, 4H), 2.11 (dd, J = 12.8, 7.3 Hz, 4H), 1.92–1.74 (m, 4H),
1.58– 1.51 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 152.47, 133.96,
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N, 6.76 (7.75).
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yl)isoindoline-1,3-dione (0.9 mmol). Complex 11 (4.9 mg, 10.0 mol%)
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1
a Z/E ratio of 70:30. H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 7.6 Hz,
2H), 7.82 (dd, J = 5.3, 2.8 Hz, 2H), 7.69 (dd, J = 5.1, 3.1 Hz, 2H), 7.54
(t, J = 7.4 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 5.49 –5.30 (m, 2H), 4.30 (t,
J = 6.6 Hz, 2H), 3.67 (t, J = 7.2 Hz, 2H), 2.15–1.98 (m, 4H), 1.75 (dt, J =
13.3, 6.8 Hz, 2H), 1.71–1.63 (m, 2H), 1.50 (dt, J = 14.7, 7.5 Hz, 2H),
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168.4, 133.8, 132.8, 132.2, 130.3, 129.5, 128.3, 123.1, 65.0, 37.9,
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405.4940, found: 428.1836. Analytical Data. Found (calcd) for:
C25H27NO4 C, 74.05 (74.00); H, 6.71 (6.66); N, 3.45 (3.40).
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