Synthesis and evaluation of Naphthalene-1, 8-dithiolate chelating ruthenium carbene catalyst for Z-Stereoretentive olefin metathesis

Article abstract of DOI:10.1016/j.jorganchem.2018.10.035

A highly Z-stereoretentive olefin metathesis ruthenium carbene catalyst containing a naphthalene-1,8-dithiol ligand was synthesized, and the structure was determined by single-crystal X-ray diffraction. The new ruthenium carbene catalyst could catalyze cross-metathesis reactions of terminal alkenes with (Z)-but-2-ene-1,4-diol to give highly Z-stereoretentive products. Like to other ruthenium carbene catalysts, the new complex tolerates many different functional groups.

Full text of DOI:10.1016/j.jorganchem.2018.10.035

Accepted Manuscript
Synthesis and evaluation of Naphthalene-1, 8-dithiolate chelating ruthenium carbene
catalyst for Z-Stereoretentive olefin metathesis
Tao Wang, Qingxiao Xie, Weijie Guo, Shutao Wu, Huiqing Zhang, Jianhui Wang
PII:
S0022-328X(18)30761-7
DOI:
https://doi.org/10.1016/j.jorganchem.2018.10.035
JOM 20620
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 31 August 2018
Revised Date: 22 October 2018
Accepted Date: 31 October 2018
Please cite this article as: T. Wang, Q. Xie, W. Guo, S. Wu, H. Zhang, J. Wang, Synthesis and
evaluation of Naphthalene-1, 8-dithiolate chelating ruthenium carbene catalyst for Z-Stereoretentive
olefin metathesis, Journal of Organometallic Chemistry (2018), doi: https://doi.org/10.1016/
j.jorganchem.2018.10.035.
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Graphic abstract

ACCEPTED MANUSCRIPT
Synthesis and Evaluation of Naphthalene-1, 8-Dithiolate Chelating
Ruthenium Carbene Catalyst for Z-Stereoretentive Olefin Metathesis
Tao Wang,a, b QingxiaoXie,a, b WeijieGuo,a, b Shutao Wu,a, b Huiqing Zhang, a, b Jianhui Wang,*, a, b
a Department of Chemistry, College of Science, Tianjin University, Tianjin 300350, P. R. China.
b Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) 30072, P. R.
China.
Abstract: A highly Z-stereoretentive olefin metathesis ruthenium carbene catalyst containing a
naphthalene-1,8-dithiol ligand was synthesized, and the structure was determined by single-crystal
X-ray diffraction. The new ruthenium carbene catalyst could catalyze cross-metathesis reactions
of terminal alkenes with (Z)-but-2-ene-1,4-diol to give highly Z-stereoretentive products. Like to
other ruthenium carbene catalysts, the new complex tolerates many different functional groups.
Key words: Ruthenium Carbene Catalyst; Naphthalene-1,8-dithiolate Chelating;
Z-Stereoretentive; Cross-metathesis Reactions.
Introduction
Olefin metathesis has become an important method of constructing C–C bonds1-4 and is
widely used to synthesize natural organic compounds, medicines, and polymers.5-10 In
general, the products gained from olefin metathesis catalyzed by traditional ruthenium
carbene olefin metathesis catalysts are mixtures of
isomer is usually the major product because it is thermodynamically preferred. However,
-olefin isomers are widely found in natural open-chain compounds (such as oleic acid and
Z- and E-olefin isomers, in which the E
Z
linoleic acid), natural macrocyclic compounds (such as civet ketone), and many
pharmaceuticals. To apply olefin metathesis as a tool for synthesizing pharmaceuticals and
natural products having
ruthenium carbene olefin metathesis catalysts to produce
selectivity during the catalysis of the olefin metathesis reaction. The design and synthesis
of -selective olefin metathesis catalysts are currently a hot research topic in the olefin
metathesis field.
Highly -selective Mo- or W-based catalysts were first developed by Shrock and
Z
-olefin frameworks,11-14 scholars must redesign traditional
Z
-olefin products with high
Z
Z
Hoveyda in 2008 and 2009. These complexes can catalyze ring-closing metathesis
reactions,15 ring-opening metathesis (ROM)/cross metathesis (CM) reactions,16
homocoupling of terminal olefin reactions,17 and ROM polymerization (ROMP) reactions
to yield high-
complex (Figure 1,
bidentate ligand. This catalyst can catalyze the CM reaction of terminal olefins to form a
high- attracted considerable
-olefin product.5,19 The successful development of catalyst
research attention because it can tolerate many functional groups and extend the
application scope of -selective olefin metathesis reactions. Altering the carboxylate ligand
and aryl group of NHC substantially decrease the activity and selectivity of the ruthenium
carbene complex, which can catalyze the CM of terminal olefins with high -selectivity
Z
-olefin products.18 In 2011, Grubbs’ group first developed a ruthenium
1
1) bearing a carbanion-appended N-heterocyclic carbene (NHC)
Z
1
Z
Z

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and good functional group adaptability.20-21 In 2013, Hoveyda’s group reported stereogenic
Ru complexes
ROM/CM processes with high efficiency and exceptional
).22 Subsequently, Hoveyda et al. found that the catalytic activity and stability of
ruthenium complex can be substantially improved when the benzene dithiolate ligand has
two ortho-chloro substitutions.23-25 Unlike bidentate ligands, complex
was developed
from commercial ruthenium catalyst in a process where one chloride is replaced by a steric
hindrance 2,4,6-triphenylbenzenethiolate ligand. Notably, catalyst displays high catalytic
activity and -selectivity as a catalyst for the homocoupling metathesis of different
terminal olefins.26 Although progress has been attained in developing catalysts for
-selective olefin metathesis reaction, ruthenium carbene complexes with new structures,
high catalytic activities, and high -selectivity remain under great demand.
3
and
4
bearing a dithiolate ligand that can be applied in ROMP and
Z
-selectivity (93:7 to >98:2
Z:E
5
6
6
Z
Z
Z
The distance of two sulfur atoms are closer in naphthalene-1, 8-dithiol than in benzene-1,
2-dithiol ligand. When naphthalene-1, 8-dithiolate is used as a bidentate ligand to coordinate with
a metal center, this ligand will have a larger geometric coordination angle than benzene-1,
2-dithiol. This larger angle may remarkably influence the catalytic activity and stereoselectivity of
the resultant complex. To examine these possible effects, we synthesized the naphthalene-1,
8-dithiolate ligand, prepared its corresponding ruthenium carbene complex, and carefully studied
the complex’s catalytic activity and Z-selectivity. Herein, we report the synthesis and catalytic
study of a Z-stereoretentive ruthenium carbene catalyst bearing a bidentate naphthalene-1,
8-dithiolate ligand.
Chart 1. Z-selective catalysts for olefin metathesis
Results and discussion
Although 1, 8-dimercaptonaphthalene27a, d and 1, 8-dimercaptohexachloronaphthalene27c have
been described in the literature, they have not been investigated extensively as ligands in
coordination chemistry.27 Some complexes bearing such ligands have found their industrial
applications, including vulcanization,28 lubricant additives,29 and catalysis.28,30 As mentioned
previously, the distance of the two sulfur atoms of naphthalene-1, 8-dithiol are closer than that of
benzene-1, 2-dithiol ligand and will result in a smaller geometric coordination angle when
coordinating with the metal center. This angle may substantially influence the catalytic activity
and stereoselectivity of the resultant complex. Given the reported ruthenium carbene catalyst
containing a benzene-1, 2-dithiol developed by Hoveyda and co-workers, we investigated the

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catalytic activity and stereoselectivity of ruthenium carbene complex bearing a naphthalene-1,
8-dithiolate ligand.
The synthesis route for the naphthalene-1, 8-dithiolate ruthenium carbene complex 9 is shown
in Scheme 1. As previously reported, the corresponding zinc naphthalene-1, 8-dithiolate 8 was
prepared with a high yield (91%) as a brown-yellow solid by reacting naphthalene-1, 8-dithiol
with zinc acetate in the presence of ethylenediamine in isopropanol.36, 37 Subsequently, zinc
naphthalene-1, 8-dithiolate (8) was reacted with commercially available ruthenium complex 7 to
obtain the desired complex 9 as a dark yellow powder at 82% yield after stirring for 3 h in THF at
1
room temperature under a nitrogen atmosphere. The H NMR spectra of the complex showed
singlet peaks at 15.35 ppm, which corresponded to the benzylidene carbene protons and indicated
that the ligand exchange was successful.
Scheme 1 Synthesis of complex 9 bearing a naphthalene-1, 8-dithiolate ligand
A single crystal of complex 9 was grown by slow evaporation from toluene at room temperature
under N2. The structure of 9 as determined by single X-ray diffraction is shown in Figure 1.
Compound 9 exhibited a slightly deformed trigonalbipyramidal structure with an NHC carbene,
two sulfides, a phenyl oxide, and a benzylidene carbene ligand seated around the Ru metal center.
The bond distances between atoms and the Ru center were as follows: Ru1–S1, 2.2719(7) Å;
Ru1–S2, 2.2804(7) Å; and Ru1–C12, 2.044(3) Å. These distances were shorter than those in 3
(Ru1–S1, 2.2933(6) Å; Ru1–S2, 2.2830(6) Å; and Ru1–C17 is 2.061(2) Å). The bond distance of
Ru1–O1 (2.3260(18) Å) was longer than that in 3 (2.2769(17) Å), and Ru1–C22 (1.831(3) Å) was
very close to 3 (Ru1–C1, 1.838(3) Å). The bond angles of S1–Ru1–S2 (93.89(3)°), C12–Ru1–S1
(88.36(7)°) and C12–Ru1–S2 (143.99(8)°) were larger than those in 3 (S2–Ru1–S1 (87.98(2)°),
C17–Ru1–S2 87.16(7)°, C17–Ru1–S1 143.40(8)°). S1–Ru1–O1 (168.85(5)°), S2–Ru1–O1
(87.98(5)°), C12–Ru1–O1 (96.59(8)°), and C22–Ru1–S1 (90.95(9)°) were smaller than those of 3
(O1–Ru1–S2, 169.84(5)°; O1–Ru1–S1, 89.77(5)°; C17–Ru1–O1, 100.46(8)°; and C1–Ru1–S2,
93.11(8)°). These results indicated that the introduction of naphthalene-1,8-dithiol changed the
steric 3D structure of the catalytic center and altered the catalytic activity, stability, and selectivity
of the catalyst.
Figure 1 Perspective view of 9. Ellipsoids are drawn at 50% probability. For clarity, the hydrogen atoms have been
omitted.
Complex 9 was stable at room temperature in CDCl3. However, when the temperature was

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raised to 50 °C, complex 9 was found to convert to complex 7 as displayed by the NMR spectra.
In fact, Hoveydas’ group has found similar phenomenon in a previous report, this may be because
of the high temperature decreased the stability of the Ru−S bond, making complex 9 derived to the
dichloride species upon exposure to CDCl3.38a, b To further study the characteristics of complex 9,
we tested the thermal stability in THF-d8 at 55 °C. The trend of decomposition is presented in
Figure 2. The decomposition of complex 9 was very fast during the first hour and gradually
retarded with time until complete decomposition after 23 h. Rapid decomposition may play a
competitive role in catalytic reaction and may be disadvantageous to the olefin metathesis
reaction.
100
Complex 9
90
80
70
60
50
40
30
20
10
0
0
2
4
6
8
10 12 14 16 18 20 22 24
Time (h)
Figure 2 Stability test of complex 9 in THF-d8 at 55 oC under N2 as monitored by 1H NMR using benzophenone as
the internal standard.
The catalytic activity and Z-selectivity of 9 for the CM reactions of terminal olefins and
(Z)-but-2-ene-1, 4-diol were then tested, and the results are shown in Table 1. The CM reactions in
THF at 55 °C in the presence of 9 (5.0 mol%) under N2 resulted in an array of Z-alkenyl alcohol
products at a relative low yield. Table 1 reveals that the Z-isomers (92:8 to 98:2 of Z/E ratios) were
the major products in all these CM reactions. Similar to other ruthenium based olefin metathesis
Table 1. Z-selectivity study of catalyst 9 in cross metathesisa,b,c
a Reaction duration: 8 h; Solvent: THF (0.5 mL); Temperature: 55 oC; Ru complex: 5 mol%; Terminal alkenes: 1.0
b
equiv.; (Z)-but-2-ene-1,4-diol: 2.0 equiv., under N2; Conversions and Z/E ratios were determined by analysis of
1H NMR spectra of the mixtures; c Yields are based on isolated products.

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catalysts, 9 could tolerate many different functional groups. For example, CM occurred between
(Z)-but-2-ene-1, 4-diol and terminal alkenes with nitro (10 and 11), aldehyde (20), ketone (14),
and unprotected amino (16) groups. Moreover, the CM reactions were successful for olefins with
different chain lengths (10 and 11; 14 and 15), and the olefins with long chains often produced
high yields. However, opposite results were observed for 17 and 18. The yield of 13 (6 carbon
chain) was obviously higher than that of 12 (3 carbon chain), but that of 19 (11 carbon chain) did
not increase significantly. Therefore, the catalytic efficiency of 9 did not change significantly after
the carbon chain length increased to a certain length.
Conclusions
A highly Z-retentive ruthenium carbene complex 9 bearing a bidentate naphthalene-1,
8-dithiolate ligand was synthesized, and the complex’s catalytic activity and Z-retentivity were
evaluated for the CM reaction of terminal alkenes and (Z)-but-2-ene-1, 4-diol. Catalyst 9 was
simple to synthesize, and its structure was determined by single X-ray diffraction. Experiment
showed that 9 could catalyze the CM reactions of terminal alkenes with (Z)-but-2-ene-1, 4-diol to
yield a high-Z-olefin product (Z/E ratios 92:8 to 98:2). Similar to other ruthenium-based catalysts,
complex 9 is suitable for many substrates and can tolerate many different functional groups.
Further work on improving the activity of this kind of catalyst by modifying the naphthalene-1,
8-dithiolate ligand is currently underway in our laboratory.
Experimental
General Procedures
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-nitrobenzene,39 1-(hex-5-en-1-yloxy)-4-nitrobenzene,39 allylben-
zoate,40 hex-5-en-1-yl benzoate,40 10-undecenyl benzoate,40 N-(5-hexenyl)phthalimide,41
2-(but-3-en-1-yl)isoindoline-1,3-dione,41 2-(but-3-en-1-yloxy)benzaldehyde,42 N-allyl-4-
nitroaniline,43 methyl 4-(but-3-en-1-yloxy)benzoate,39 methyl 4-(hex-5-en-1-yloxy) ben-
zoate39). All other reagents and solvents were purchased and 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; tetrahydrofuran and toluene were distilled from sodium and
1
benzophenone. TMEDA was distilled from calcium hydride. H and 13C NMR data were
recorded on 400 MHz spectrometer with CDCl3 as solvent. The chemical shifts are
reported in ppm relative to CDCl3 (δ = 7.26) for 1H NMR and relative to the central CDCl3
1
resonance (δ = 77.0) for 13C NMR. Coupling constants (
J
) are quoted in Hz for H.
Multiplicities are reported as follows: singlet (s), doublet (d), doublet of doublets (dd),
1
triplet (t), quartet (q), and multiplet (m). Conversions were obtained by H NMR analysis
of the sample. NMR data of known compounds 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 were determined
by isolated products.

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General Procedure for Preparation of Compound 8 and 9
.
Preparation of Zinc 1, 8-Naphthalenedithiolate (8). A mixture of 1,8-naphthalenedithiol
.
(150 mg, 0.78 mmol, 1.00equiv), Zn(OAc)2 2H2O (684 mg, 3.12 mmol, 4.00 equiv) and
ethylenediamine (0.31 mL, 4.68 mmol, 6.00 equiv.) in
i-PrOH (10 mL) was allowed to stir
for 3 hours at room temperature. The precipitated solid was filtered, washed with methanol
(15.0 mL) and chloroform (15.0 mL), and dried to afford
as brown-yellow solid.
8 (182 mg, 0.71 mmol, 91% yield)
Preparation of Complex 9. To a 10 mL oven-dried vial charged with a stir bar and zinc
1,8-naphthalenedithiolate (d) (153.4 mg, 0.60 mmol, 2.00 equiv) under N2 atmosphere, a
solution of complex
7 (188 mg, 0.30 mmol, 1.00 equiv) in tetrahydrofuran (2 mL) was
added. The mixture was stirred 3 hours at room temperature. Solvent was removed under
vacuum, and then the residual tetrahydrofuran was removed through co-evaporation with
n
-hexane (3 x 3 mL). The acquired solid was purified by silica gel column chromatography
(CH2Cl2) in a glovebox and recrystallized from toluene to afford 183.5 mg of the desired
1
compound (82%). H NMR (400 MHz, CDCl3) δ 15.35 (s, 1H), 7.70 (d,
J
= 7.4 Hz, 1H),
7.34 (d,
6.96 (s, 1H), 6.93 (d,
6.64 (d, = 6.6 Hz, 1H), 6.03 (s, 1H), 5.02 (dt,
= 15.2, 7.7 Hz, 2H), 3.68 (s, 1H), 2.60 (d,
(s, 6H), 1.59 (d, = 6.6 Hz, 3H), 1.50 (s, 3H), 1.42 (d,
J
= 7.3 Hz, 1H), 7.22 (d,
J = 3.3 Hz, 1H), 7.12 (d, J = 5.1 Hz, 1H), 7.09 (s, 1H),
J
= 7.9 Hz, 2H), 6.81 (dt,
J
= 11.9, 7.6 Hz, 2H), 6.74 – 6.68 (m, 2H),
J
J = 13.1, 6.5 Hz, 1H), 4.04 (s, 1H), 3.88 (dd,
J
J
= 16.7 Hz, 6H), 2.51 (d,
J = 3.8 Hz, 3H), 2.16
J
J
= 6.5 Hz, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ 154.08, 141.27, 140.87, 138.41, 137.91, 137.68, 136.97, 136.45, 135.57,
130.53, 130.10, 128.35, 126.73, 126.44, 124.61, 123.84, 123.38, 122.92, 121.83, 115.34,
79.16, 52.46, 51.40, 23.94, 21.83, 21.46, 19.33, 19.11, 17.33 ppm. IR (KBr): ν 3442, 3037,
2998, 2971, 2952, 2900, 1606, 1585, 1573, 1538, 1477, 1447, 1428, 1406, 1390, 1368,
1352, 1317, 1282, 1262, 1193, 1183, 1139, 1111, 1065, 1028, 989, 923, 879, 842, 805, 754,
737, 696, 568, 544, 415. ESI-MS [M]+ calcd for C41H45N2O1Ru1S2: 747.0140; found:
747.1944. CCDC: 1580720.
General Procedure for Experimental Procedure for
Metathesis (CM) Reactions.
Z-Stereoselective Cross-
General Procedure for Cross-metathesis (Table 1): 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
-2-butene-1,4-diol (0.30 mmol, 2.0 equiv) under N2 atmosphere. The mixture was
(5.0 mol %) in tetrahydrofuran (0.3 mL) and then was vigorously
added a solution of
9
stirred for 8 hours at 55 °C to the end of the reaction. Organic solvent was removed in
vacuo, and then the residue was purified by silica gel column chromatography (30 % Et2O
in hexanes to 50 % Et2O in hexanes) to give the desired product.
The Characterization of The Olefin Matathesis Products 10-20 23
(
Z
)-5-(4-Nitrophenoxy)-2-pentene-1-ol (10): Pale yellow oil in 96:4
Z
/
E
ratio (34 %
1
yield). H NMR (400 MHz, CDCl3) δ 8.13 (d,
5.76 (dt, = 12.3, 6.8 Hz, 1H), 5.58 (q, = 7.9 Hz, 1H), 4.19 (d,
= 6.3 Hz, 2H), 2.57 (q,
= 6.6 Hz, 2H), 1.55 (s, 1H) ppm. 13CNMR (100 MHz, CDCl3) δ
163.7, 131.71, 127.49, 125.97, 114.42, 67.87, 58.45, 27.36 ppm.
)-7-(4-Nitrophenoxy)-2-pentene-1-ol (11): Yellow oil in 97:3
1H NMR (400 MHz, CDCl3) δ 8.20 (d,
= 9.2 Hz, 2H), 6.94 (d, = 9.2 Hz, 2H), 5.66 (dt,
J = 8.6 Hz, 2H), 6.87 (d,
J
= 8.6 Hz, 2H),
J
J
J = 6.6 Hz, 2H), 4.01 (t, J
J
(
Z
Z/E ratio (35 % yield).
J
J
J

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= 13.2, 6.6 Hz, 1H), 5.61 – 5.51 (m, 1H), 4.22 (d,
J
= 6.5 Hz, 2H), 4.06 (t,
J = 6.4 Hz, 2H),
2.18 (q,
J
= 7.3 Hz, 2H), 1.89 – 1.79 (m, 2H), 1.57 (p, J
= 7.6 Hz, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ 164.12, 141.38 132.23, 129.10, 125.92, 114.39, 68.59, 58.54, 28.49, 27.02,
25.93 ppm. ESI-MS [M+Na]+ calcd for C13H17NO4: 251.2820, found: 274.1042. Analytical
Data. Found (calcd) for: C13H17NO4 C, 62.14 (62.27); H, 6.82 (6.88); N, 5.57(5.50).
(
Z
)-4-Hydroxyhept-2-en-1-yl Benzoate (12): Yellow oil in 97:3
1H NMR (400 MHz, CDCl3) δ 8.04 (d,
= 7.1 Hz, 2H), 7.57 (t,
= 7.7 Hz, 2H), 5.92 (dt, = 12.1, 6.6 Hz, 1H), 5.76 (dt, = 11.1, 7.0 Hz, 1H), 4.94 (d,
6.9 Hz, 2H), 4.34 (d,
166.66, 133.55, 133.12, 130.03, 129.64, 128.40, 125.64, 60.60, 58.55 ppm.
Z/E ratio (21 % yield).
J
J
= 7.4 Hz, 1H), 7.44 (t,
J
J
J
J
=
J
= 6.5 Hz, 2H), 1.71 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ
(
Z
)-7-Hydroxyhept-5-en-1-yl Benzoate (13): Pale yellow oil in 92:8
Z
J
/
E
ratio (38 %
1
yield). H NMR (400 MHz, CDCl3) δ 7.96 (d,
7.36 (t, = 7.4 Hz, 2H), 5.57 (dt, = 12.4, 7.1 Hz, 1H), 5.46 (q,
(t, = 6.5 Hz, 2H), 4.13 (d, = 6.5 Hz, 2H), 2.08 (q, = 7.1 Hz, 2H), 1.70 (dt,
Hz, 3H), 1.46 (p,
= 7.2 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 166.69, 132.91,
132.30, 130.34, 129.55, 129.06, 128.36, 64.76, 58.56 , 28.22, 26.96, 25.93 ppm.
)-2-(5-Hydroxyhept-3-enyl)-isoindoline-1,3-dione (14): Yellow oil in 97:3
J = 7.6 Hz, 2H), 7.48 (t,
= 7.3 Hz, 1H),
J
J
J
= 8.3, 7.9 Hz, 1H), 4.25
= 13.7, 6.4
J
J
J
J
J
(
Z
Z
/
E
ratio
= 5.4, 3.0 Hz, 2H), 7.72 (dd,
5.4, 3.1 Hz, 2H), 5.75 – 5.67 (m, 1H), 5.60 – 5.51 (m, 1H), 4.15 (d, = 6.7 Hz, 2H), 3.76 (t,
= 7.1 Hz, 2H), 2.51 (q,
= 7.0 Hz, 2H), 1.72 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ
1
(26 % yield). H NMR (400 MHz, CDCl3) δ 7.84 (dd,
J
J =
J
J
J
168.39, 133.99, 132.01, 131.69, 127.95, 123.26, 58.29, 37.49, 26.53 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).
(
Z
)-2-(7-Hydroxyhept-5-enyl)-isoindoline-1,3-dione (15): Yellow oil in 96:4
(31 % yield). 1H NMR (400 MHz, CDCl3) δ 7.91 – 7.78 (m, 2H), 7.72 (d,
= 4.5 Hz, 2H),
5.65 (q, = 7.6, 6.8 Hz, 1H), 5.49 (q, = 8.1 Hz, 1H), 4.21 (d, = 6.3 Hz, 2H), 3.69 (t,
6.9 Hz, 2H), 2.16 (q, = 6.9 Hz, 2H), 1.70 (dd, = 14.9, 7.2 Hz, 3H), 1.51 – 1.39 (m, 2H)
Z/E ratio
J
J
J
J
J =
J
J
ppm. 13C NMR (100 MHz, CDCl3) δ 168.48, 133.94, 132.09, 132.07, 129.21, 123.22,
58.47, 37.59, 27.76, 26.57, 26.40 ppm.
(
Z
)-4-((4-Nitrophenyl)amino)but-2-en-1-ol (16): Yellow oil in 98:2
Z
/
E
ratio (28 %
= 9.3, 2.6 Hz, 2H), 6.73 – 6.37 (m, 2H),
= 8.7, 8.2 Hz, 1H), 4.66 (s, 1H), 4.32 (d, = 6.3 Hz, 2H),
= 6.4 Hz, 2H), 1.65 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ 152.94, 132.41,
1
yield). H NMR (400 MHz, CDCl3) δ 8.09 (dd,
5.97 – 5.80 (m, 1H), 5.68 (q,
3.92 (d,
J
J
J
J
127.77, 126.40, 111.26, 58.58, 40.61, 29.32 ppm. ESI-MS [M+Na]+ calcd for C10H12N2O3:
208.1270, found: 231.0741. Analytical Data. Found (calcd) for: C10H12N2O3 C, 57.69
(57.72); H, 5.81 (5.75); N, 13.45 (13.35).
Methyl-(
ratio (21 % yield). 1H NMR (400 MHz, CDCl3) δ 8.08 – 7.81 (m, 2H), 6.90 – 6.76 (m, 2H),
5.82 – 5.68 (m, 1H), 5.66 – 5.52 (m, 1H), 4.18 (d, = 6.8 Hz, 2H), 3.97 (t, = 6.4 Hz, 2H),
3.81 (s, 3H), 2.54 (q,
= 6.4 Hz, 2H), 1.60 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ
Z)-4-((5-hydroxypent-3-en-1-yl)oxy)benzoate (17): Colorless oil in 97:3 Z/E
J
J
J
166.83, 162.45, 131.62, 131.48, 127.96, 122.77, 114.06, 67.18, 58.40, 51.88, 27.48 ppm.
ESI-MS[M+Na]+calcd for C13H16O4: 236.2670; found: 259.0933. Analytical Data. Found
(calcd) for: C13H16O4 C, 66.09 (66.02); H, 6.83 (6.72).

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Methyl-(
Z
)-4-((7-hydroxyhept-5-en-1-yl)oxy)benzoate (18): Colorless oil in 94:6 Z/E
ratio (18 % yield). 1H NMR (400 MHz, CDCl3) δ 7.98 (d,
J
= 8.9 Hz, 2H), 6.90 (d,
= 6.7, 1.2 Hz, 2H), 4.01 (t,
= 7.4 Hz, 2H), 1.86 – 1.77 (m, 2H), 1.61 – 1.53 (m,
J = 8.9
Hz, 2H), 5.69 – 5.61 (m, 1H), 5.61 – 5.51 (m, 1H), 4.21 (dd,
J
J
= 6.4 Hz, 2H), 3.88 (s, 3H), 2.17 (q,
J
3H) ppm. 13C NMR (100 MHz, CDCl3) δ 162.83, 132.44, 131.58, 129.28, 128.96, 122.45,
114.05, 67.89, 58.59, 51.84, 28.63, 27.08, 26.03 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).
(Z)-12-Hydroxydodec-10-en-1-yl Benzoate (19): Colorless oil in 98:2 Z/E ratio (37 %
1
yield). H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.3 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H),
7.44 (t, J = 7.7 Hz, 2H), 5.60 (dt, J = 12.6, 6.4 Hz, 1H), 5.54 (dd, J = 12.6, 5.3 Hz, 1H),
4.31 (t, J = 6.7 Hz, 2H), 4.19 (d, J = 6.3 Hz, 2H), 2.06 (q, J = 7.0 Hz, 2H), 1.76 (p, J = 6.7
Hz, 2H), 1.45 (dd, J = 14.3, 6.7 Hz, 4H), 1.35 (s, 4H), 1.29 (s, 5H) ppm. 13C NMR (100
MHz, CDCl3) δ 166.73, 133.13, 132.82, 130.50, 129.53, 128.39, 128.33, 65.14, 58.60,
29.59, 29.45, 29.39, 29.25, 29.18, 28.71, 27.43, 26.02 ppm.
(Z)-2-((5-Hydroxypent-3-en-1-yl)oxy)benzaldehyde (20): Pale yellow oil in 96:4 Z/E
1
ratio (28 % yield). H NMR (400 MHz, CDCl3) δ 10.44 (s, 1H), 7.82 (d,
7.54 (t, = 7.8 Hz, 1H), 7.04 (t, = 7.4 Hz, 1H), 6.98 (d, = 8.4 Hz, 1H), 5.81 (dt,
6.7 Hz, 1H), 5.71 – 5.61 (m, 1H), 4.27 (d, = 6.5 Hz, 2H), 4.12 (t, = 6.3 Hz, 2H), 2.67 (q,
= 6.4 Hz, 2H), 1.69 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ 189.90, 161.04, 135.92,
J
= 7.6 Hz, 1H),
J
J
J
J
= 12.4,
J
J
J
131.51, 128.95, 127.64, 124.98, 120.84, 112.57, 67.75, 58.53, 27.54 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).
Corresponding Author
*E-mail (J. Wang): wjh@tju.edu.cn.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant No.
21572155 and 21372175)
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•
•
•
•
Naphthalene-1,8-dithiolate chelating Ru-carbene catalyst was synthesized.
Single-crystal X-ray diffraction was tested to determine the catalyst.
The catalyst can catalyze CM reactions to give highly Z-stereoretentive products.
The new complex tolerates many different functional groups.