Synthesis, catalysis, and DFT study of a ruthenium carbene complex bearing a 1,2-dicarbadodecaborane (12)-1,2-dithiolate ligand

Article abstract of DOI:10.1039/c8dt04290j

A ruthenium carbene catalyst containing a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand was synthesized, and the structure was determined by single crystal X-ray diffraction. This new ruthenium carbene catalyst can catalyze the ring opening metathesis polymerization (ROMP) reaction of norbornene to give the corresponding Z-polymer (Z/E ratio, 98:2) in high yield (93%); ring opening cross metathesis (ROCM) reactions of norbornene/5-norbornene-2-exo, 3-exo-dimethanol with styrene or 4-fluorostyrene to give the corresponding Z-olefin products (Z/E ratios, 97:3-98:2), respectively, in high yields (73%-88%); cross metathesis (CM) reactions of terminal alkenes with (Z)-but-2-ene-1,4-diol to give high Z-olefin products in low yields; homometathesis reactions of terminal alkenes to give olefin products in low yields. Like other ruthenium carbene catalysts, the new complex tolerates many different functional groups. DFT calculations were also performed in order to understand the process of forming Z-olefin products and the decomposition process of catalysts.

Full text of DOI:10.1039/c8dt04290j

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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DOI: 10.1039/C8DT04290J
Journal Name
ARTICLE
Synthesis, Catalysis, and DFT Study of A Ruthenium Carbene
Complex Bearing A 1,2-Dicarbadodecaborane (12)-1,2-Dithiolate
Ligand
Received 00th January 20xx,
Accepted 00th January 20xx
Tao Wang,a, b Botao Wu,*, b, c, d Weijie Guo,a, b Shutao Wu,a, b Huiqing Zhang,a, b Yanfeng Dang*, a, b
DOI: 10.1039/x0xx00000x
Jianhui Wang*, a, b
www.rsc.org/
Ruthenium carbene catalyst containing a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand was synthesized, and the
structure was determined by single crystal x-ray diffraction. This new ruthenium carbene catalyst can catalyze ring opening
metathesis polymerization (ROMP) reaction of norbornene to give the corresponding Z-polymer (Z/E ratio, 98:2) in high
yield (93%); ring opening cross metathesis (ROCM) reactions of norbornene/5-norbornene-2-exo, 3-exo-dimethanol with
styrene or 4-fluorostyrene to give the corresponding Z-olefin products (Z/E ratios, 97:3-98:2), respectively, in high yields
(73%-88%); Cross metathesis (CM) reactions of terminal alkenes with (Z)-but-2-ene-1,4-diol to give high Z-olefin products
in low yields. Homometathesis reactions of terminal alkenes to give olefin products in low yields. Like other ruthenium
carbene catalysts, the new complex tolerates many different functional groups. DFT calculation was also performed in
order to understand the process of forming Z-olefin products and the decomposition process of catalysts.
Z-olefin structures, a critical challenge for olefin metathesis
reactions is the production of Z-olefin products.
In this context, some new metathesis catalysts with Z-
Introduction
The olefin metathesis reaction is a simple, fast, and efficient
tool for constructing complex molecules. These reactions
usually produce few by-products, which is important from a
green chemistry standpoint. Olefin metathesis has been widely
applied to many synthetic fields, including synthetic
chemicals,1 pharmaceuticals and biotechnology,2 functional
polymer materials.3 The success of olefin metathesis has
stemmed from the discovery of air and moisture stable
ruthenium carbene catalysts which are tolerant to many
different functional groups.4 These catalysts are highly
selective for E-olefin products in cross metathesis (CM)
reactions and in the construction of macrocyclic compounds
via ring closing metathesis (RCM) reactions. However, since
many natural products and pharmaceutical molecules5 contain
selectivity have been developed. For example, a molybdenum
aryloxy complex 1 (Chart 1) with a pyrryl ligand has been found
to give some Z-olefin products in ring-opening cross-
metathesis (ROCM) reactions.6 Subsequently, a series of Z-
selective complexes containing molybdenum or tungsten were
developed using a similar structure,7 and these complexes
were successfully applied to the synthesis of macrocyclic
8b
molecules through CM and RCM reactions8a,
. Some
molybdenum- and tungsten-based catalysts show excellent Z-
selectivity and high reactivity, especially in sterically hindered
systems. In addition to biological products, a tungsten oxo
alkylidene catalyst has been demonstrated to promote ring-
closing metathesis reactions to form 45-membered macrocycle
compounds with Z-selectively.8c These works on molybdenum
and tungsten catalysts has enhanced the development of
ruthenium carbene catalysts. In 2011, a ruthenium-based Z-
selective olefin metathesis catalyst 2 (Chart 1) was developed.9
Complex 2 can catalyze CM reactions of terminal olefins to
give Z-olefin dimer products with excellent selectivity. Further
studies have shown that complex 3 (Chart 1),10 which is
formed by replacing the carboxyl in 2 with a nitrate ligand, has
better catalytic activity and selectivity than 2. Using a more
hindered NHC ligand also increases the activity and Z-
selectivity of the catalyst.11 These Z-selective catalysts can be
used in a wide variety of CM reactions, including the synthesis
of industrial products.12 In addition these ruthenium based
a. Department of Chemistry, College of Science, Tianjin University, Tianjin 300350, P.
R. China. E-mail: wjh@tju.edu.cn, yanfeng.dang@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
DOI: 10.1039/x0xx00000x
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catalysts tolerate many functional groups, and efficiently Similar example for steric protection against VinewuAcrlteicolepOhnililnice
DOI: 10.1039/C8DT04290J
convert olefins in different solvents and at various attack at the benzylidene carbon has been reported by Fogg et
temperatures while maintaining excellent Z-selectivity.13 The al.24 Under this context, a new ruthenium carbene catalyst
development of these Z-selective ruthenium carbene catalysts bearing a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand
has further expanded the range of olefin metathesis reactions. was synthesized and the catalytic activity of this complex is
In the quest to further expand the scope of metathesis reported herein.
reactions, complex 4a (Chart 1), in which the two chlorides of
the Hoveyda-Grubbs second generation catalyst were
substituted with a benzene dithiolate ligand was developed in
2013.14 This catalyst was found to catalyze the ring opening
Results and discussion
The new Ru complex containing 1,2-dicarbadodecaborane (12)-
metathesis reaction of a substrate with a highly strained cyclic
olefin to give a Z-selective product. Later on, complexes 4b-e
(Chart 1) with substituted benzene dithiolate ligands were
found to have even better stabilities and catalytic activities.15
These complexes all have good functional group tolerance and
give highly Z-olefin products in the CM reactions of (Z)-but-2-
ene-1,4-diol and terminal alkenes. These ruthenium dithiolate
catalysts have simple structures which are easily constructed
and they have good functional groups tolerance. Thus they
have good prospects for future applications.15-18
1,2-dithiolate ligand could be synthesized via two different
pathways, which are depicted in Scheme 1. In the first pathway,
1,2-dicarbadodecaborane(12)-1,2-dithiol was first converted to the
corresponding zinc salt (6) in high yield (87%). The zinc salt 6 was
then treated with the Hoveyda-Grubbs second generation catalyst
(8) in THF at room temperature to give the desired product 9 in a 65%
yield. In the second pathway, 1,2-dicarbadodecaborane(12)-1,2-
dithiol was treated with sodium tert-butoxide (1:2 equivalent ) in
CH3OH at room temperature to quantitatively give sodium 1,2-
dicarbadodecaborane(12)-1,2-dithiolate (7) in a high yield (93%).
The sodium dithiolate 7 and 8 were stirred in THF at 22 °C for two
hours to give the ruthenium based complex 9 as an orange-brown
Chart 1. Z-selective catalysts for olefin metathesis
1
solid in good yield (72%). The H NMR spectra of the complex
MesN
O
N
contained singlet peaks at values of δ1.43-2.60 ppm, and 15.55 ppm
which correspond to the carborane and benzylidene carbene
protons respectively. This indicates that the ligand exchange was
successful.
N
Ph
N
Mo
t-Bu
C
Ru
O
O
Br
-iPrO
Br
TBSO
Scheme 1. Synthesis of 1,2-dicarbadodecaborane(12)-1,2-dithiolate
chelating ruthenium carbene catalyst 9
2
1
MesN
H
NMes
X
S
N
NMes
Cl
Cl
Mes
H
R
X
Zn(OAc)2
Zn
MesN
N
Ru
S
N
N
S
Mes
Mes
O
Ru
S
O
-O N+
R
SH
SH
H
Ru
6
Ru
S
S
O
8
O
THF, r.t
O
-iPrO
SNa
SNa
4a; X = H, R = H
4b; X = Br, R = H
4c; X = Cl, R = H
4d; X = Me, R = H
4e; X = F, R = F
5
9
t-BuONa
3
7
Mes = 2,4,6-trimethylphenyl
= BH; = CH, or C
Carborane is a polyhedron composed of carbon and boron
atoms. Due to the special bonding characteristics of boron, the
electrons are delocalized over the whole polyhedron and the
compound is as stable as benzene. However, the electron
deficient property of borane gives caborane a stronger
electron withdrawing property than benzene when
functionalized at carbon atoms.19, 20 For example, the acidity of
1-hydroxy-1,2-dicarbadodecaborane, in which the hydroxyl
group is linked to a 1,2-dicarbadodecaborane, is between 4-
nitrophenol and 2,4-dinitrophenol.21 Moreover, carborane
possesses a three-dimensional polyhedron structure which is
more sterically hindered that the planar structure of a benzene
ring,22 and carboranes were often used in ligand design and
catalysis.23 1,2-dicarbadodecaborane has large space
constraints, and plays an electron withdrawing effect when
contacting at carbon atoms. These two properties may
increase the stability of the catalyst by weakening the
nucleophilic properties of sulfur atoms and inhibiting the
nucleophilic reaction of sulfur atoms to benzylidene carbon.
A single crystal of the complex 9 was grown by slow evaporation
from a CH2Cl2/n-hexane mixture solution at -5 °C under N2. The
structure of 9 determined by single X-ray diffraction is shown in
Figure 1. The arrangement of the ligand around the metal center is
similar to that found in Hoveyda complexes.18 Compound 9 has a
slightly deformed trigonalbipyramidal structure with the NHC
carbene, two sulfide, the phenyl oxide, and the benzylidene
carbene ligand seated around the Ru metal center. The bond
distance between the sulfur and the Ru center Ru1-S1 is 2.2813 (7)
Å which is longer than that in 4b [2.247 (2) Å], 4c [2.2706 (10) Å]
and 4e [2.2759 (5) Å], but little short than 4a [2.2830 (6) Å]. Ru1-S2
[2.3215 (7) Å] is longer than that in 4a [2.2933 (6) Å]，4b [2.295 (2)
Å], 4c [2.2954 (9) Å] and 4e [2.3160 (5) Å]. The S1-Ru1-S2 [91.75 (2)o]
bond angles is larger than the corresponding angles in 4a [87.98
(2)o], 4b [88.17 (7)o], 4c [88.23 (3)o] and 4e [88.740 (16)o]. These
results show that the introduction of a 1,2-dicarbadodecaborane
(12)-1,2-dithiol tag changed the structure of the catalytic center.
2 | J. Name., 2012, 00, 1-3
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Next, the catalytic activity and Z-stereoretentiveVioewf A9rticfloerOnCliMne
reactions of terminal olefins and (Z)-but-2-ene-1,4-diol were tested
DOI: 10.1039/C8DT04290J
and the results are shown in Table 2. The CM reactions in THF at
60 °C in the presence of 9 (5.0 mol%) under N2 proceeded smoothly
to give an array of Z-alkenyl alcohols. The products all had high
stereoretentives (Z:E 85:15 to 97:3). Like other ruthenium based
olefin metathesis catalysts, 9 tolerate many different functional
groups. For example, CM occurred between (Z)-but-2-ene-1,4-diol
and terminal alkenes with hydroxyl (16 and 18), ketone (18), and
aldehyde (17, 26) groups. In addition the CM reaction was
successful for olefins with different chain lengths (20-22) and longer
chains gave higher yield. Non-conjugated olefins with alkyl chains
(15-22) were more active and had better Z-product selectivity than
conjugated olefins with aryl groups (23 and 24).
Figure 1 Perspective view of 9. Ellipsoids are drawn at the 50% probability.
For clarity, the solvents and all hydrogen atoms have been omitted. See the
supporting materials for detailed bond lengths and angles (Å).
Table 2 Z-stereoretentive study of Ru-based catalyst 9 in CM
reactions of different terminal alkenes and (Z)-but-2-ene-1,4-diol
The catalytic activity of 9 to the ring opening metathesis
polymerization (ROMP) reaction of norbornene (10) was initially
detected. The results were shown in Table 1. ROMP of 10 in the
presence of 9 (0.1 mol%) gave the corresponding Z-polymer
(11)(Z/E ratio, 98:2) in high yield (93%). When the loading of
catalyst was reduced to 0.005 mol%, the turnover number (TON) of
the catalyst 9 reached up to 5900. Next, the ring opening cross
metathesis (ROCM) reaction of 10 with styrene or 4-fluorostyrene
5.0 mol% Ru-Cat.
THF, 60 o
G
HO
OH
G
OH
+
C
CHO
O
OH
O2N
O
OH
S
OH
OH
a, b, c
15
16
17
, 38 (34)%; 90:10
, 41 (38)%; 95:5
OH
, 35 (31)%; 87:13
O
O
O
OH
N
4
OH
OH
O
O
Table 1 Z-selective ROMP and ROCM of Ru-based catalyst for
norbornene and 5-norbornene-2-exo, 3-exo-dimethanol
18
19
22
20
, 31 (28)%; 96:4
, 36 (32)%; 93:7
O
, 44 (41)%; 95:5
O
F3C
G
9
Ru complex
+
O
4
O
9
G
OH
OH
OH
1.0 equiv.
substrate
20.0 equiv.
23
, 33 (28)%; 97:3
21
24
, 52 (49)%; 97:3
, 48 (45)%; 96:4
NO2
entry
1a,c,d
G
cat.
product
con./yield Z/E
>99%/93% 98:2
44%/28% 98:2
0.1 mol%
0.005 mol%
------
n
OHC
O
4
OH
OH
10
10
O
OH
11
12
4
1 mol%
3 mol%
>99%/42% 98:2
>99%/73% 98:2
a. C6H5
, 30 (24)%; 91:9
25, 44(41)%; 97:3
2b,c,d
26
, 42 (40)%; 85:15
1 mol%
3 mol%
1 mol%
3 mol%
1 mol%
3 mol%
G
>99%/36% 98:2
>99%/77% 98:2
>78%/51% 97:3
>99%/88% 98:2
>83%/46% 98:2
>99%/80% 98:2
b. 4-FC6H4
a. C6H5
a Reaction duration: 6 h; Solvent: THF (0.5 mL); Temperature: 60 oC; Ru complex: 5 mol%;
Terminal alkenes: 1.0 equiv.; (Z)-but-2-ene-1,4-diol: 2.0 equiv., under N2;
b Conversions and Z/E were determined by analysis of 1H NMR spectra of the mixtures;
c Yields are based on isolated pure products.
OH
OH
HO
3b,c,d
G
exo
13a
b. 4-FC6H4
HO
OH
Table 3 Z-selective cross-metathesis of Ru-based catalyst for
terminal olefins
14
HO
4b,c,d
a. C6H5
------
---/---
---/---
------
------
5 mol%
R
R
R
10 mol% Ru-Cat.
endo
13b
+
C2H4
b. 4-FC6H4
THF, 60 o
C
------
5 mol%
O
O
N
a Solvent: CH2Cl2; time: 1h; temperature: 22 oC; b Solvent: THF; time: 1h; temperature:
40 oC; c Conversions and Z/E were determined by analysis of 1H NMR spectra of the
mixtures; d Yields are based on isolated pure products.
O
O
O
O
N
2
2
O
O
2
2
30 (27)%a; 76:24b
32 (28)%; 71:29
27,
28,
o
using 9 as the catalyst in THF at 40 C were studied. The desired
O2
N
O
O
NO2
O2
N
O
O
NO2
olefin products with high Z/E ratios (98:2) were obtained in 42%
and 36%, respectively, at low loading of 9 (1.0 mol%). However, it
respectively gave 73% and 77% yields of olefin products with high
Z/E ratios (98:2) when the catalyst loading was increased to 3.0
mol%. Similarly, the ROCM reactions of 5-norbornene-2-exo, 3-exo-
dimethanol (13a) with styrene or 4-fluorostyrene using complex 9
(3 mol%) as the catalyst also gave the desired Z-products in 88%
and 80% respectively. These results are comparable to those of
4a.14 However, 5-norbornene-2-endo, 3-endo-dimethanol does not
undergo ROCM reactions with styrene or 4-fluorostyrene, even
using considerable amount of 9 at elevated temperatures. The
results indicate that the steric hindrance of the substrate plays an
important role in the catalytic reaction.
3
3
29,
30c
,
35 (31)%; 84:16
38 (35)%; 75:25
O
O
OHC
O
O
CHO
3
3
3
3
NO2
O2N
31,
36 (32)%; 78:22
32,
28 (26)%; 65:35
NC
O
O
CN
3
3
33,
24 (20)%; 84:16
a Except where noted, the catalytic reactions were performed in THF (0.5 mL) at 60 oC for 8 h under
9
nitrogen in the presence of (5 mol%).
b Conversions and Z/E were determined by analysis of 1H NMR spectra of the unpurified mixtures.
c Yields are based on isolated pure products.
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DOI: 10.1039/C8DT04290J
Figure 2 Reaction pathway of propene convert to (Z)-2-butene and S-shift decomposition with Gibbs free energy of all intermediates and
transition states by calculated
During the catalyst 9-mediated CM reactions between terminal endergonicity during olefin coordination (3.6 kcal/mol vs. 5.1
olefins and (Z)-but-2-ene-1,4-diol, occasionally small amounts of the kcal/mol).
terminal olefins homocoupled products were observed. So,
In 2015, Hoveyda’s group15 suggested that the catalyst
homometathesis reactions of terminal olefins were investigated decomposition pathway may involve a sulfide shift leading to
using 9 as the catalyst (Table 3, 27 to 33). Although the dimeric generation of a catalytically inactive Ru-alkyl species. Figure 2 also
olefin products were obtained in relatively low yields, the Z-olefin shows this decomposition mechanism after propene coordinates to
products were found as the major isomers (Z:E 65:35 to 84:16). The the Ru (II) center of complexes 9 and 4a. The free-energy barrier of
homocoupling metathesis yields of olefins with aldehyde (32) and the sulfide shift in complex 9 with o-carboranedithiol as the ligand
cyano (33) substituent are lower than that of olefin having other is 11.7 kcal/mol, which is larger than the corresponding barrier of
substituents. However, Z-olefin isomers were found as the major the product of Z-selective (6.7 kcal/mol) metathesis; the latter
product in these reactions, indicating that catalyst 9 is able to further presents advantages in ΔG≠ compared with the sulfide shift
selectively generate Z-olefin products without inheriting the original process (15.1 kcal/mol vs. 15.3 kcal/mol). In addition, the product
configuration of the substrates.
of Z-selective metathesis is more thermodynamically stable than
For simplification, propene was selected as the model molecule that of sulfide-shift decomposition (7.1 kcal/mol vs. 13.0 kcal/mol).
for the metathesis reactions and the activated catalyst 9 and 4a as However, when catechothiolate is applied as the catalyst ligand, the
CH3CH=[Ru] carbene complex was considered to represent complex free-energy barrier of the sulfide shift is only 6.9 kcal/mol, which is
9 and 4a. The schematic pathways of the continuous coupling lower than the free-energy barrier of Z-selective metathesis (6.9
metathesis of complex 9 with propene leading to (Z)-2-butene are kcal/mol vs. 7.8 kcal/mol). The same finding is obtained by
indicated as the blue line in Figure 2. We sought to determine inspecting the ΔG≠ of the sulfide-shift decomposition and Z-
whether replacement of catechothiolate by o-carboranedithiol as selective metathesis pathways (12.0 kcal/mol vs. 14.4 kcal/mol).
the catalyst ligand could reduce the rate of catalyst decomposition; The product of Z-selective metathesis is more thermodynamically
thus, complex 4a, which was previously studied by Hoveyda’s unstable than that obtained from sulfide-shift decomposition (6.0
group15, was also considered here, as indicated by the red line in kcal/mol vs. 2.8 kcal/mol), resulting in side reactions and
Figure 2. Acidity is an evident difference between the two ligands, deactivation of the Z-selective metathesis catalyst.
and the low electron density of o-carboranedithiol causes low
Interestingly, replacement of catechothiolate with o-
carboranedithiol could substantially improve the stability of the
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molecular sieves (Aldrich) and were either saturated with dry
DOI: 10.1039/C8DT04290J
argon or degassed before use. Reactions were monitored by
analytical thin layer chromatography on 0.20 mm Yantai
Huagong silica gel plates. Silica gel (200-300 mesh) (from
Yantai Huagong Company) was used for flash chromatography.
CDCl3 and DMSO-d6 were purchased from TCI and used as
catalyst. A catalyst is more prone to decomposition with
catechothiolate as a ligand, and its stability and Z-selectivity may
decrease during reaction.
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Conclusions
In summary, a 1,2-dicarbadodecaborane(12)-1,2-dithiolate received.
1-(but-3-enoxyl)-4-nitrobenzoate25,
hexenyl)phthalimide26,
1-[4-hydroxy-3-(2-propen-1-
yl)phenyl]ethanone27, 2-propenyl benzoate28, 5-hexenyl
benzoate29, benzoate30,
10-undecenyl 1,2-
N-(5-
chelating Ru carbene catalyst 9 with high activity and Z-
selectivity was synthesized. Although the core structure of 9 is
similar to those of reported benzene disulfide chelated
analogues, the activity and selectivity of 9 is different which is
due to the strongly electron deficient nature and steric
bulkiness of the 1,2-dicarbadodecaborane(12) ligand. Catalyst
9 can catalyze the ROMP/ROCM reactions to give high yields
and Z/E ratios. The CM reactions of terminal alkenes with (Z)-
but-2-ene-1,4-diol, or homo-metathesis of terminal alkenes
using 9 as catalyst also gave Z-olefins as major products. Like
other ruthenium-based catalysts, 9 is able to tolerate many
different functional groups and is suitable for many substrates.
dicarbadodecaborane(12)-1,2-dithiol (5)31, 2-(allylthio)phenol32,
2-(but-3-en-1-yloxy)benzaldehyde33. All other chemicals or
reagents were obtained from commercial sources.
In order to evaluate the stability of the catalyst in the
reaction, the formation of Z-products, and the decomposition
of catalysts were performed by using DFT calculations. All
calculations were performed using Gaussian 09 package34.
Geometry optimizations were performed at the theory level of
B3LYP-D3BJ35-37/LanL2dz38 for Ru and 6-31G(d)39 for other
atoms in the gas phase. Frequency correction factors40 were
used for thermal corrections to Gibbs free energy after
frequency calculations at the same level. Single-point
electronic energy calculations were performed at the level of
M06-D341/def2-TZVP42 for Ru and 6-311+G (2df, 2p) for other
atoms, and in conjunction with the SMD43 model to account
The introduction of
a 1,2-dicarbadodecaborane(12)-1,2-
dithiolate ligand to the Ru center improved the stability and
reactivity of the catalyst, which were consistent with the DFT
calculations. In addition, this work provides a theoretical basis
for the synthesis and design of other efficient metal catalysts.
Further, studies on the application of this 1,2-
dicarbadodecaborane (12)-1,2-dithiolate chelating Ru carbene
catalyst to the synthesis of functional molecules and polymers for the solvation effect of THF. The Computed structures were
illustrated by using CYL View44.
is currently ongoing in our this laboratories.
Experimental details
Preparation of zinc 1,2-dicarbadodecaborane(12)-1,2-
dithiolate (6): In an N2 filled glove box, a solution of
Zn(OAc)2•2H2O (878 mg, 4.00 mmol, 2.0 equiv.)
andethylenediamine (0.40 mL, 6.00 mmol, 3.0 equiv.) in i-PrOH
(8 mL) is transferred to a vial containing 5 (416.6 mg, 2.00
mmol, 1.0 equiv.), and the resulting mixture is allowed to stir
for 1h at 22 °C. The precipitated solid was filtered, washed
with methanol (5.0 mL) and hot chloroform (5.0 mL), and dried
in a vacuum to afford zinc 1,2-dicarbadodecaborane(12)- 1,2-
dithiolate (6) (472.7 mg, 1.74 mmol, 87% yield) as white solid.
Preparation of sodium 1,2-dicarbadodecaborane(12)-1,2-
dithiolate (7): In an N2 filled glove box, a solution of sodium
tert-butoxide (427.1 mg, 4.40 mmol, 2.2 equiv.) in methanol
(8.2 mL) is transferred to a vial containing 5 (416.6 mg, 2.00
mmol, 1.0 equiv.), and the resulting mixture is allowed to stir
for 30 minutes at 50 °C. The mixture is cooled to room
temperature followed by evaporation of solvent under vacuum.
The residue is transferred to a fritted funnel and washed with
tetrahydrofuran (10 mL). After removal of solvents in vacuo, 7
is obtained as white solid (469.1 mg, 1.86 mmol, 93% yield). 7
may contain a small amount of impurities, such as boric acid
and deboronated cluster {C2B9}. These impurities are difficult
to separate, but they do not affect the next reaction, so the
sodium salt can be directly carried out in the next reactions
Experimental
General Procedures
1H-NMR and 13C-NMR spectra were acquired in CDCl3 on
Bruker (AVANCE III) 600 MHz or Bruker (AVANCE III ) 400 MHz
spectrometers. If not otherwise noted, chemical shift values of
are reported as values in ppm relative to residual CDCl3 (J
1
=7.26) for H-NMR spectra, relative to CDCl3 (77.1 ppm) for
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).
Coupling constants (J) are quoted in Hz. at 400 MHz or 600
1
MHz for H. High-resolution mass spectra were provided using
Bruker Daltonics matrix assisted laser desorption tandem time
of flight mass spectrometry the (Autoflex tof/tof III). High-
resolution mass spectra (HRMS) were obtained on a JEOL JMS-
DX303 instrument. Elemental analyses were performed by the
Elemental Analysis Section of Tianjin University.
Materials and Methods
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. Toluene, THF, hexane and Et2O was distilled from
sodium/benzophenone under a N2 atmosphere. Methanol was
distilled over MgSO4. CH2Cl2 was dried over CaH2, and distilled
prior to use. All other solvents were dried over 4-8 Å mesh
1
without further purification. H{11B} (400 MHz, MeOD) δ 2.53
(s, 4H), 2.14 (s, 2H), 1.69-1.63 (d, J = 23.0 Hz, 4H). 13C{1H} NMR
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
(100 MHz, MeOD-d4) δ 102.20 ppm. 11B NMR (128 MHz, HRMS [M]+ calcd for C33H48B10N2ORuS2: 762.3255; found:
View Article Online
DOI: 10.1039/C8DT04290J
MeOD-d4) δ -2.60, -3.75, -6.89, -7.84, -9.98, -11.05, -12.14, - 762.3226.
13.30 ppm. δ IR (KBr): ν 3608, 3539, 2588, 2561, 2060, 1626, Z-Selective ROMP Reaction
1444, 1305, 1067, 1050, 1006, 972, 944, 889, 727, 516 cm-1.
An oven-dried 10 mL vial equipped with a magnetic stir bar
Preparation of Ru-based dithiolate complex (9): To a 2-dram is charged with 0.1 mL CH2Cl2 solution which contain complex 9
vial charged with stir bar and sodium 1,2- (0.8 mg, 0.001 mmol), then a solution of norbornene (94.2 mg,
a
dicarbadodecaborane(12)-1,2-dithiolate (60.5 mg, 0.24 mmol, 1.0 mmol) in 1.5 mL CH2Cl2 is added. The solution is stir for 1 h
1.2 equiv.) under N2 atmosphere, a solution of Ru complex 8 at room temperature and the solution becomes very viscous.
(125.2 mg, 0.20 mmol, 1.0 equiv.) in tetrahydrofuran (4.0 mL) Then MeOH (5 mL) is added, the white poly-norbornene
is added. The resulting mixture is allowed to stir at 22 °C for settles out with vigorous stirring. The polymer washed with
three hours, and then the solvent is evaporated under vacuum. MeOH (4 mL x 3) and dried under vacuum for 1 h to provide a
1
Residual tetrahydrofuran is removed through co-evaporation white solid 11 (87.5 mg, yield 93%) in 98:2 ratio. H NMR (400
with pentane (2 x 4 mL). The resulting solid is dissolved in MHz, CDCl3) δ 5.32 – 5.11 (m, 2H), 2.81 (dd, J = 12.3, 9.6 Hz,
dichloromethane and passed through a short column of Celite 2H), 1.97 – 1.86 (m, 1H), 1.86 – 1.72 (m, 2H), 1.46 – 1.25 (m,
(4 cm in height), placed in a pipette (0.5 cm diameter), with 2H), 1.02 (dd, J = 22.7, 10.4 Hz, 1H). 13C NMR (100 MHz, CDCl3)
dichloromethane (10 mL). The filtrate is adsorbed onto fresh δ 133.87, 42.71, 38.61, 33.21.
Celite and subjected to vacuum until complete dryness. The
An oven-dried 50 mL vial equipped with a magnetic stir bar
adsorbed material is loaded onto a second short column of is charged with 0.1 mL CH2Cl2 solution which contain complex
Celite (4 cm in height) and washed with Et2O (20 mL), after 9 (0.8 mg, 0.001 mmol), then a solution of norbornene (2.0 g,
which Ru-based complex is collected upon elution with 21.2 mmol) in 10 mL CH2Cl2 is added. The solution is stir for 1 h
dichloromethane. After removal of solvents and co- at room temperature and the solution becomes gelatinous
evaporation with pentane, Ru-Based dithiolate complex (9) is form. Then MeOH (10 mL) is added, the white poly-
isolated as an orange-brown solid (109.8 mg, 0.14 mmol, 72% norbornene settles out with vigorous stirring. The polymer
yield). 1H NMR (400 MHz, CDCl3) δ 15.55 (s, 1H, Ru=CH), 7.32 – washed with MeOH (10 mL x 3) and dried under vacuum for 8
7.27 (m, 1H, PhH), 7.12 (d, 3JH,H = 6.1 Hz, 2H, PhH), 7.01 (d, 3JH,H h to provide a white solid 11 (0.5555 g, yield 28%, TON 5900)
= 8.3 Hz, 1H, PhH), 6.88 (s, 1H, PhH), 6.82 (t, 3JH,H = 7.4 Hz, 1H, in 98:2 ratio. 1H NMR (400 MHz, CDCl3) δ 5.32 – 5.11 (m, 2H),
PhH), 6.71 (d, 3JH,H = 6.6 Hz, 1H, PhH), 5.95 (s, 1H, PhH), 5.16 – 2.81 (dd, J = 12.3, 9.6 Hz, 2H), 1.97 – 1.86 (m, 1H), 1.86 – 1.72
3
5.02 (m, 1H, CH(CH3)2), 3.96 (dd, JH,H = 22.1, 10.7 Hz, 2H, N- (m, 2H), 1.46 – 1.25 (m, 2H), 1.02 (dd, J = 22.7, 10.4 Hz, 1H).
3
3
CH2), 3.73 (t, JH,H = 9.8 Hz, 2H, N-CH2), 2.58 (d, JH,H = 15.9 Hz, 13C NMR (100 MHz, CDCl3) δ 133.87, 42.71, 38.61, 33.21.
3
6H, PhCH3), 2.44 (s, 3H, PhCH3), 2.17 (d, JH,H = 4.1 Hz, 6H, Z-Selective ROCM Reactions
PhCH3), 1.69 (d, JH,H = 6.7 Hz, 3H, CH3(CHCH3)), 1.64 (s, 3H, General Procedure: An oven-dried 10 mL vial equipped with a
PhCH3), 1.44 (d, JH,H = 6.6 Hz, 3H, CH3(CHCH3)) ppm. 13C{1H} magnetic stir bar is charged with alkene substrate (1.0 equiv.)
3
3
NMR (100 MHz, CDCl3): δ 259.35, 214.90, 154.52, 141.23, and terminal olefin (20 equiv.) in a fume hood. The vial is then
139.41, 138.37, 136.12, 135.74, 135.13, 134.51, 130.88, 129.96, sealed, evacuated and purged with N2. To this vessel, a
129.16, 128.06, 123.83, 122.12, 115.66, 96.97 (C-o-carborane), solution of complex 9 (1.0-3.0 mol%) in THF is added. The
o
86.14, 83.26, 51.84, 51.21, 23.92, 21.29, 21.09, 20.28, 19.17, resulting solution is allowed to stir for 6 hours at 40 C, after
18.26, 17.06 ppm. 11B NMR (128 MHz, CD3CN) δ -3.16, -7.63, - which the reaction is concentrated in vacuum. Purification is
8.65, -10.08, -11.12, -12.21 ppm. 11B{1H} NMR (128 MHz, performed through silica gel chromatography.
acetone-d6) δ -3.03, -6.47, -7.76, -9.36, -11.03 ppm. 1H{11B} ((Z)-2-((1S,3R)-3-Vinylcyclopentyl)vinyl)benzene
(12a):
NMR (400 MHz, CDCl3) δ 15.53 (s, 1H, Ru=CH), 7.26 (m, 1H, Complex 9 (3.0 mol%) dissolve in 0.2 mL THF was used. The
PhH), 7.09 (d, 3JH,H = 7.8 Hz, 2H, PhH), 6.98 (d, 3JH,H = 8.3 Hz, 1H, product was purified by column chromatography with hexane
PhH), 6.86 (s, 1H, PhH), 6.79 (t, 3JH,H = 7.4 Hz, 1H, PhH), 6.68 (d, to provide a colorless oil (22.9 mg, yield 73%) in 98:2 Z/E ratio.
3JH,H = 7.3 Hz, 1H, PhH), 5.93 (s, 1H, PhH), 5.06 (dt, 3JH,H = 13.4, 1H NMR (400 MHz, CDCl3) δ 7.38 – 7.29 (m, 2H), 7.29 – 7.17 (m,
6.6 Hz, 1H, CH(CH3)2), 3.94 (dd, 3JH,H = 23.7, 10.4 Hz, 2H, N-CH2), 3H), 6.36 (d, J = 11.5 Hz, 1H), 5.82 (ddd, J = 17.4, 10.2, 7.4 Hz,
3
3.74 (d, JH,H = 21.5 Hz, 2H, N-CH2), 2.65 (S, 1H, BH), 2.57 (d, 1H), 5.58 (dd, J = 11.5, 10.1 Hz, 1H), 4.94 (dddd, J = 34.5, 10.2,
3JH,H = 14.9 Hz, 6H, PhCH3), 2.44 (s, 3H, PhCH3), 2.33 (S, 1H, BH), 1.9, 1.1 Hz, 2H), 3.16 – 2.93 (m, 1H), 2.64 – 2.43 (m, 1H), 2.09 –
2.22 (S, 2H, BH), 2.17 (d, 3JH,H = 5.8 Hz, 6H, PhCH3), 2.03 (S, 1H, 1.97 (m, 1H), 1.97 – 1.76 (m, 2H), 1.54 – 1.43 (m, 2H), 1.27 –
3
BH), 1.80 (S, 1H, BH), 1.68 (d, JH,H = 6.7 Hz, 3H, CH3(CHCH3)), 1.17 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 143.07, 137.90,
1.64 (s, 3H, PhCH3), 1.58 (S, 2H, BH), 1.44 (d, 3JH,H = 6.5 Hz, 3H, 128.63, 128.16, 127.63, 126.51, 112.58, 44.58, 41.48, 38.72,
CH3(CHCH3)), 1.42 (S, 1H, BH), 1.34 (S, 1H, BH) ppm. IR (KBr): ν 33.06, 31.96.
3446, 3051, 2981, 2919, 2606 (B-H), 2578 (B-H), 2559 (B-H), (Z)-1-Fluoro-4-(2-((1S,3R)3-vinylcyclopentyl)vinyl)benzene
1608, 1588, 1575, 1478, 1452, 1427, 1388, 1374, 1308, 1282, (12b): Complex 9 (3.0 mol%) dissolve in 0.2 mL THF was added.
1266, 1185, 1111, 1033, 917, 848, 755, 731, 576, 419 cm-1. The product was purified by column chromatography with
hexane to provide a colorless oil (26.4 mg, yield 77%) in 98:2
6 | J. Name., 2012, 00, 1-3
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Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 7.33 – 7.15 (m, 2H), 7.11
ARTICLE
(Z)-2-((4-Hydroxybut-2-en-1-yl)thio)phenol (16V)i:ewTArhtiicsle Ownlianes
DOI: 10.1039/C8DT04290J
– 6.91 (m, 2H), 6.32 (d, J = 11.5 Hz, 1H), 5.83 (ddd, J = 17.4, purified by column chromatography to provide yellow oil (yield
10.2, 7.4 Hz, 1H), 5.58 (dd, J = 11.3, 10.2 Hz, 1H), 4.96 (dddd, J 31%) in 87:13 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J =
= 33.9, 10.2, 1.8, 1.1 Hz, 2H), 3.10 – 2.90 (m, 1H), 2.64 – 2.45 7.6 Hz, 1H), 7.27 (t, J = 7.5 Hz, 1H), 6.98 (d, J = 8.2 Hz, 1H), 6.87
(m, 1H), 2.12 – 1.96 (m, 1H), 1.96 – 1.78 (m, 2H), 1.58 – 1.44 (t, J = 7.4 Hz, 1H), 5.83 – 5.47 (m, 2H), 4.24 – 3.93 (m, 2H), 3.72
(m, 2H), 1.23 (dt, J = 12.4, 10.4 Hz, 1H). 13C NMR (100 MHz, (d, J = 5.6 Hz, 2H), 3.36 (d, J = 7.0 Hz, 2H) ppm. 13C{1H} NMR
CDCl3) δ 162.75, 160.31, 142.95, 137.89, 133.79, 130.11, (100 MHz, CDCl3) δ 158.02, 136.76, 132.11, 131.62, 126.62,
126.52, 115.12, 114.91, 112.65, 44.56, 41.39, 38.58, 32.99, 120.35, 117.96, 115.27, 57.68, 32.93 ppm. ESI-MS [M+Na]+
31.93.
calcd for C10H12O2S: 196.2640, found: 219.0448. Analytical
3-((Z)-Styryl)-5-vinylcyclopentane-1, 2-diyl)dimethanol (14a): Data. Found (calcd) for: C10H12O2S C, 61.20 (61.15); H, 6.16
Complex 9 (3.0 mol%) dissolve in 0.2 mL THF was added. The (6.22).
product was purified by column chromatography with
(Z)-2-((5-Hydroxypent-3-en-1-yl)oxy)benzaldehyde (17): This
hexane/ether (3/7) to provide a colorless oil (22.0 mg, yield was purified by column chromatography to provide colorless
88%) in 98:2 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 7.36 – 7.28 oil (yield 34%) in 90:10 Z/E ratio. H NMR (400 MHz, CDCl3) δ
1
(m, 2H), 7.27 – 7.19 (m, 3H), 6.47 (d, J = 11.5 Hz, 1H), 5.74 (ddd, 10.44 (s, 1H, PhCHO), 7.82 (d, J = 7.6 Hz, 1H), 7.54 (t, J = 7.8 Hz,
J = 17.8, 10.1, 7.8 Hz, 1H), 5.52 (dd, J = 11.5, 10.2 Hz, 1H), 5.09 1H), 7.03 (t, J = 7.4 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 5.91 – 5.74
– 4.91 (m, 2H), 3.64 (d, J = 18.3 Hz, 2H), 3.60 – 3.40 (m, 3H), (m, 1H), 5.66 (dd, J = 17.7, 7.9 Hz, 1H), 4.27 (d, J = 6.2 Hz, 2H),
3.28 (s, 1H), 2.73 (ddd, J = 16.7, 10.4, 6.4 Hz, 1H), 2.24 – 2.15 4.12 (t, J = 6.3 Hz, 2H), 2.67 (dd, J = 13.3, 6.6 Hz, 2H), 1.86 (s,
(m, 1H), 2.15 – 2.06 (m, 2H), 2.06 – 1.95 (m, 1H), 1.36 (dd, J = 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 190.01, 161.05,
23.3, 11.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 141.40, 137.44, 136.02, 131.53, 128.96, 127.63, 124.89, 120.84, 112.54, 67.71,
135.81, 129.80, 128.41, 126.75, 114.54, 61.92, 50.45, 48.48, 58.51, 27.53 ppm. ESI-MS [M+Na]+ calcd for C12H14O3:
46.32, 40.14, 39.77.
3-((Z)-4-Fluorostyryl)-5-vinylcyclopentane-1,2-diyl)dimeth-
206.2410, found: 229.0835. Analytical Data. Found (calcd) for:
C12H14O3 C, 69.89 (69.96); H, 6.84 (6.87).
anol (14b): Complex 9 (3.0 mol%) dissolve in 0.2 mL THF was (Z)-1-(4-hydroxy-3-(4-hydroxybut-2-en-1-yl)phenyl)ethan-1-
added. The product was purified by column chromatography one (18)15: This was purified by column chromatography to
1
with hexane/ether (3/7) to provide a colorless oil (21.5 mg, provide off-white solid (yield 32%) in 93:7 Z/E ratio. H NMR
1
yield 80%) in 98:2 Z/E ratio. H NMR (400 MHz, CDCl3) δ 7.18 (600 MHz, CDCl3) δ 7.79 (d, J = 2.0 Hz, 1H), 7.74 (dd, J = 8.4, 2.1
(dd, J = 8.4, 5.5 Hz, 2H), 7.00 (t, J = 8.7 Hz, 2H), 6.42 (d, J = 11.5 Hz, 1H), 6.84 (d, J = 8.4 Hz, 1H), 5.77 (dd, J = 11.6, 5.5 Hz, 1H),
Hz, 1H), 5.73 (ddd, J = 17.8, 10.1, 7.8 Hz, 1H), 5.50 (dd, J = 11.3, 5.67 (dd, J = 18.6, 8.0 Hz, 1H), 4.36 (d, J = 6.5 Hz, 1H), 3.52 (d, J
10.3 Hz, 1H), 5.08 – 4.93 (m, 2H), 3.62 (d, J = 3.3 Hz, 2H), 3.62 – = 7.9 Hz, 1H), 2.54 (d, J = 6.8 Hz, 1H), 1.36 – 1.19 (m, 1H). 13C
3.44 (m, 4H), 2.79 – 2.57 (m, 1H), 2.25 – 2.15 (m, 1H), 2.11 (dd, NMR (150 MHz, CDCl3) δ 197.68, 159.87, 131.86, 131.25,
J = 9.3, 5.8 Hz, 2H), 1.97 (dt, J = 12.4, 6.1 Hz, 1H), 1.35 (dd, J = 129.67, 129.36, 127.57, 125.87, 115.84, 68.00, 58.37, 29.71,
23.3, 11.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 162.83, 160.38, 26.30, 25.60.
141.27, 135.83, 133.41, 130.06, 128.68, 115.29, 115.08, 114.63, (Z)-2-(7-hydroxyhept-5-en-1-yl)isoindoline-1,3-dione
(19)15:
This was purified by column chromatography to provide yellow
oil (yield 41%) in 95:5 Z/E ratio. H NMR (600 MHz, CDCl3) δ
61.85, 50.40, 48.42, 46.31, 40.06, 39.71.
Z-Selective CM Reactions
1
General Procedure: An oven-dried 10 mL vial equipped with a 7.83 (dd, J = 5.4, 3.1 Hz, 2H), 7.70 (dd, J = 5.4, 3.0 Hz, 2H), 5.69
magnetic stir bar is charged with alkene substrate (1.0 equiv.) – 5.57 (m, 1H), 5.54 – 5.42 (m, 1H), 4.20 (d, J = 6.8 Hz, 2H), 3.80
and Z-2-butene-1,4-diol (2.0 equiv.) in a fume hood. The vial is – 3.45 (m, 2H), 2.20 – 1.99 (m, 2H), 1.75 (s, 1H), 1.73 – 1.59 (m,
then sealed, evacuated and purged with N2. To this vessel, a 2H), 1.51 – 1.37 (m, 2H). 13C NMR (150 MHz, CDCl3) δ 168.51,
solution of Ru-based complex (5.0 mol %) in tetrahydrofuran 133.96, 132.09, 129.22, 123.24, 58.48, 37.58, 27.76, 26.56,
(0.5 mL) is added. The resulting solution is allowed to stir for 8 26.39.
hours at 60 oC, after which the reaction is concentrated in (Z)-4-hydroxybut-2-en-1-yl benzoate (20)45: This was purified
1
vacuo (percent conversion determined by 400 MHz H NMR by column chromatography to provide yellow oil (yield 28%) in
1
analysis). Purification is performed through silica gel 96:4 Z/E ratio. H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 7.7 Hz,
chromatography.
2H), 7.59 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 5.95 (dt, J =
(Z)-5-(4-nitrophenoxy)pent-2-en-1-ol (15)15: This was 13.0, 7.7 Hz, 1H), 5.84 – 5.62 (m, 1H), 4.96 (d, J = 7.0 Hz, 2H),
purified by column chromatography to provide brown oil (yield 4.36 (d, J = 6.5 Hz, 2H), 2.16 (s, 1H). 13C NMR (150 MHz, CDCl3)
38%) in 95:5 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 8.25 – 8.07 δ 166.69, 133.58, 133.15, 130.01, 129.66, 128.43, 125.62,
(m, 1H), 6.99 – 6.87 (m, 1H), 5.88 – 5.75 (m, 1H), 5.73 – 5.53 60.61, 58.54.
(m, 1H), 4.25 (d, J = 6.7 Hz, 1H), 4.08 (t, J = 6.4 Hz, 1H), 2.63 (q, (Z)-12-Hydroxydodec-10-en-1-yl benzoate (21): This was
J = 6.7 Hz, 1H), 1.60 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 163.77, purified by column chromatography to provide pale yellow oil
1
131.72, 127.48, 125.93, 114.44, 67.90, 58.47, 27.38.
(yield 49%) in 97:3 Z/E ratio. H NMR (400 MHz, CDCl3) δ 8.05
(d, J = 7.8 Hz, 2H), 7.55 (t, J = 7.3 Hz, 1H), 7.44 (t, J = 7.5 Hz, 2H),
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5.66 – 5.56 (m, 1H), 5.56 – 5.44 (m, 1H), 4.31 (t, J = 6.6 Hz, 2H), NMR (100 MHz, CDCl3) δ 190.85, 164.16, 132.27, 132.01,
View Article Online
DOI: 10.1039/C8DT04290J
4.19 (t, J = 5.1 Hz, 2H), 2.06 (dd, J = 13.7 Hz, 6.8, 2H), 1.81 – 129.83, 129.08, 114.75, 68.13, 58.54, 28.56, 27.05, 25.98. ESI-
1.72 (m, 2H), 1.54 (s, 1H), 1.49 – 1.40 (m, 2H), 1.35(m, 4H), MS [M+H]+ calcd for C14H18O3: 234.1256, found: 235.1329.
1.29 (s, 6H) ppm; 13C{1H} NMR (150 MHz, CDCl3) δ166.76, Analytical Data. Found (calcd) for: C14H18O3 C, 71.77 (71.76); H,
133.23, 132.84, 130.50, 129.55, 128.34, 65.15, 58.63, 29.72, 7.74 (7.72).
29.59, 29.46, 29.39, 29.25, 29.18, 28.71, 27.43, 26.02 ppm. ESI- (Z)-dec-5-ene-1,10-diyl dibenzoate (27): This was purified by
MS [M+Na]+ calcd for C19H28O3: 304.4220, found: 327.1937. column chromatography to provide pale yellow oil (yield 27%)
1
Analytical Data Found (calcd) for: C19H28O3 C, 74.96 (74.83); H, in 76:24 Z/E ratio. H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.3
9.27 (9.21).
Hz, 4H), 7.55 (t, J = 7.4 Hz, 2H), 7.44 (t, J = 7.6 Hz, 4H), 5.41 (t, J
(Z)-7-Hydroxyhept-5-en-1-yl benzoate (22): This was purified = 4.6 Hz, 2H), 4.32 (t, J = 6.5 Hz, 4H), 2.12 (dd, J = 12.6, 7.0 Hz,
by column chromatography to provide pale yellow oil (yield 4H), 1.82 – 1.70 (m, 4H), 1.52 (dt, J = 14.9, 7.5 Hz, 4H). ppm.
1
45%) in 96:4 Z/E ratio. H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 13C{1H} NMR (150 MHz, CDCl3) δ 166.70, 132.87, 130.45,
7.7 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.7 Hz, 1H), 5.68 130.33, 129.81, 129.55, 128.35, 64.99, 64.94, 32.16, 28.35,
– 5.60 (m, 1H), 5.59 – 5.51 (m, 1H), 4.33 (t, J = 6.6 Hz, 1H), 4.21 28.21, 26.85, 26.13, 25.96 ppm. ESI-MS [M+Na]+ calcd for
(d, J = 6.6 Hz, 1H), 2.17 (q, J = 7.3 Hz, 1H), 1.81 – 1.76 (m, 1H), C24H28O4: 380.4840, found: 403.1882. Analytical Data. Found
1.67 (s, 1H), 1.54 (dt, J = 15.0, 7.5 Hz, 1H) ppm. 13C{1H} NMR (calcd) for: C24H28O4 C, 75.76 (75.75); H, 7.42 (7.39).
(100 MHz, CDCl3) δ 166.72, 132.93, 132.32, 130.36, 129.56, (Z)-2,2'-(dec-5-ene-1,10-diyl)bis(isoindoline-1,3-dione)
(28):
129.06, 128.38, 64.76, 58.57, 28.21, 26.95, 25.93 ppm. ESI-MS This was purified by column chromatography to provide brown
1
[M+Na]+ calcd for C14H18O3: 234.2950, found: 257.1154. oil (yield 28%) in 71:29 Z/E ratio. H NMR (400 MHz, CDCl3) δ
Analytical Data. Found (calcd) for: C14H18O3 C, 71.77 (71.62); H, 7.85 (dd, J = 5.4, 3.0 Hz, 4H), 7.72 (dd, J = 5.4, 3.0 Hz, 4H), 5.37
7.74 (7.88).
(dt, J = 9.4, 4.2 Hz, 2H), 3.69 (td, J = 7.3, 2.7 Hz, 4H), 2.08 (dd, J
(Z)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-ol (23)15: This was = 12.7, 7.2 Hz, 4H), 1.69 (dd, J = 15.1, 7.5 Hz, 4H), 1.41 (dt, J =
purified by column chromatography to provide pale yellow oil 15.1, 7.5 Hz, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ 168.48,
1
(yield 28%) in 97:3 Z/E ratio. H NMR (600 MHz, CDCl3) δ 7.60 133.86, 132.16, 130.21, 129.66, 123.18, 37.91, 32.07, 28.18,
(d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 6.59 (d, J = 11.8 Hz, 28.08, 26.86, 26.71 ppm. ESI-MS [M+Na]+ calcd for C26H26N2O4:
1H), 6.08 – 5.93 (m, 1H), 4.42 (d, J = 6.4 Hz, 2H), 1.66 (s, 1H). 430.5040, found: 453.1781. Analytical Data. Found (calcd) for:
13C NMR (150 MHz, CDCl3) δ 139.99, 133.19, 129.82, 129.34, C26H26N2O4 C, 72.54 (72.56); H, 6.09 (6.11); N, 6.51 (6.48).
128.99, 126.50, 125.23, 123.33, 59.48.
(Z)-1,6-bis(4-nitrophenoxy)hex-3-ene (29): This was purified by
(Z)-3-phenylprop-2-en-1-ol (24)46: This was purified by column column chromatography to provide brown oil (yield 31%) in
chromatography to provide pale yellow oil (yield 24%) in 91:9 84:16 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 9.2 Hz,
1
Z/E ratio. H NMR (600 MHz, CDCl3) δ 7.35 (t, J = 7.6 Hz, 2H), 4H), 6.96 (d, J = 9.2 Hz, 4H), 5.69 (t, J = 4.8 Hz, 2H), 4.12 (t, J =
7.30 – 7.24 (m, 1H), 7.21 (d, J = 7.6 Hz, 2H), 6.58 (d, J = 11.7 Hz, 6.5 Hz, 4H), 2.67 (dd, J = 12.0 Hz, 6.3 Hz, 4H) ppm. 13C{1H} NMR
1H), 5.88 (dt, J = 12.5, 6.4 Hz, 1H), 4.45 (d, J = 6.4 Hz, 2H), 1.55 (100 MHz, CDCl3) δ 163.86, 141.59, 127.55, 125.94, 114.41,
(s, 1H). 13C NMR (150 MHz, CDCl3) δ 136.51, 131.11, 128.80, 68.00, 27.37 ppm. ESI-MS [M+Na]+ calcd for C18H18N2O6:
128.29, 127.30, 59.75.
358.3500, found: 381.1056. Analytical Data. Found (calcd) for:
(Z)-7-(2-nitrophenoxy)hept-2-en-1-ol (25): This was purified by C18H18N2O6 C, 60.33 (60.30); H, 5.06 (5.04); N, 7.82 (7.81).
column chromatography to provide pale yellow oil (yield 41%) (Z)-1,10-bis(4-nitrophenoxy)dec-5-ene (30): This was puri-fied
1
in 97:3 Z/E ratio. H NMR (400 MHz, CDCl3) δ 7.79 (dd, J = 8.1, by column chromatography to provide white solid (yield 35%)
1
1.7 Hz, 1H), 7.49 (ddd, J = 9.0, 7.5, 1.7 Hz, 1H), 7.07 – 7.02 (m, in 75:25 Z/E ratio. H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 9.2
1H), 7.02 – 6.95 (m, 1H), 5.67 – 5.57 (m, 1H), 5.57 – 5.48 (m, Hz, 1H), 7.01 – 6.82 (m, 1H), 5.56 – 5.32 (m, 1H), 4.05 (t, J = 6.4
1H), 4.18 (d, J = 6.4 Hz, 2H), 4.09 (t, J = 6.2 Hz, 2H), 2.14 (q, J = Hz, 1H), 2.17 – 2.11 (m, 1H), 2.08 (dd, J = 11.6, 6.7 Hz, 1H), 2.08
7.4 Hz, 2H), 1.87 – 1.78 (m, 2H), 1.61 (s, 1H), 1.60 – 1.52 (m, (dd, J = 11.6, 6.7 Hz, 1H), 1.82 (dt, J = 12.8, 5.7 Hz, 1H), 1.61 –
2H). 13C NMR (100 MHz, CDCl3) δ 152.38, 134.04, 132.25, 1.47 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 164.18, 141.37,
129.08, 125.51, 120.15, 114.47, 69.34, 58.52, 28.45, 26.95, 130.31, 129.76, 125.90, 114.39, 68.71, 32.13, 28.43, 25.80
25.87. ESI-MS [M+H]+ calcd for C13H17NO4: 251.1158, found: ppm. ESI-MS [M+H]+ calcd for C22H26N2O6: 414.1791, found:
252.1236. Analytical Data. Found (calcd) for: C13H17NO4 C, 415.1860. Analytical Data. Found (calcd) for: C22H26N2O6 C,
62.14 (62.12); H, 6.82 (6.79); N, 5.57 (5.55).
63.76 (63.74); H, 6.32 (6.30); N, 6.76 (7.73).
(Z)-4-((7-hydroxyhept-5-en-1-yl)oxy)benzaldehyde (26): This (Z)-1,10-bis(2-nitrophenoxy)dec-5-ene (31): This was purified
was purified by column chromatography to provide pale by column chromatography to provide white solid (yield 32%)
1
yellow oil (yield 40%) in 85:15 Z/E ratio. H NMR (400 MHz, in 78:22 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 7.80 (dd, J = 8.1,
CDCl3) δ 9.86 (s, 1H), 7.88 – 7.72 (m, 2H), 6.97 (d, J = 8.7 Hz, 1.6 Hz, 2H), 7.54 – 7.44 (m, 2H), 7.06 (d, J = 8.4 Hz, 2H), 7.02 –
2H), 5.71 – 5.60 (m, 1H), 5.55 (dt, J = 11.0, 7.3 Hz, 1H), 4.20 (d, 6.95 (m, 2H), 5.52 – 5.34 (m, 2H), 4.10 (td, J = 6.3, 2.4 Hz, 4H),
J = 6.5 Hz, 2H), 4.03 (t, J = 6.4 Hz, 2H), 2.16 (dd, J = 14.6, 7.3 Hz, 2.17 – 1.97 (m, 4H), 1.82 (dd, J = 8.6, 6.6 Hz, 4H), 1.56 (dd, J =
2H), 1.87 – 1.77 (m, 2H), 1.67 (s, 1H), 1.60 – 1.52 (m, 2H). 13C 15.0, 7.6 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ 152.48, 140.01,
8 | J. Name., 2012, 00, 1-3
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6
7
I. Ibrahem, M. Yu, R. R. Schrock and A. H. Hoveyda, J. Am.
133.96, 130.34, 129.82, 125.48, 120.00, 114.47, 69.49, 32.02,
28.34, 25.66. ESI-MS [M+H]+ calcd for C22H26N2O6: 414.1791,
found: 415.1860. Analytical Data. Found (calcd) for: C22H26N2O6
C, 63.76 (63.77); H, 6.32 (6.31); N, 6.76 (7.75).
View Article Online
Chem. Soc., 2009, 131, 3844-3845.
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Hoveyda, J. Am. Chem. Soc., 2014, 136, 16493-16496. (b) S. J.
Meek, R. V. OBrien, J. Llaveria, R. R. Schrock and A. H.
Hoveyda, Nature, 2011, 471, 461-466.
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and A. H. Hoveyda, J. Am.Chem. Soc., 2014, 136, 16136-
16139. (b) M. Yu, C. B. Wang, A. F. Kyle, P. Jakubec, D. J.
Dixon, R. R. Schrock and A. H. Hoveyda, Nature, 2011, 479,
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(Z)-4,4'-(dec-5-ene-1,10-diylbis(oxy))dibenzaldehyde (32): This
was purified by column chromatography to provide white solid
(yield 26%) in 65:35 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 9.90
(s, 2H), 7.84 (d, J = 8.7 Hz, 4H), 7.00 (d, J = 8.7 Hz, 4H), 5.53 –
5.36 (m, 2H), 4.06 (t, J = 6.4 Hz, 4H), 2.10 (dd, J = 11.6, 6.8 Hz,
4H), 1.91 – 1.77 (m, 4H), 1.62 – 1.51 (m, 4H). 13C NMR (100
MHz, CDCl3) δ 190.77, 164.21, 131.98, 130.32, 129.79, 114.74,
68.25, 32.16, 28.58, 26.87, 25.94. ESI-MS [M+H]+ calcd for
C24H28O4: 380.1988, found: 381.2057. Analytical Data. Found
(calcd) for: C24H28O4 C, 75.76 (75.74); H, 7.42 (7.38).
(Z)-4,4'-(dec-5-ene-1,10-diylbis(oxy))dibenzonitrile (33): This
was purified by column chromatography to provide white solid
(yield 20%) in 84:16 Z/E ratio. 1H NMR (400 MHz, CDCl3) δ 7.59
(d, J = 8.8 Hz, 4H), 6.95 (d, J = 8.8 Hz, 4H), 5.43 (t, J = 4.7 Hz,
2H), 4.02 (t, J = 6.4 Hz, 4H), 2.14 (dd, J = 12.7, 7.2 Hz, 4H), 1.89
– 1.77 (m, 4H), 1.55 (dd, J = 15.1, 7.4 Hz, 4H). 13C NMR (100
MHz, CDCl3) δ 162.38, 133.97, 129.76, 119.25, 115.16, 110.85
– 110.65, 103.80, 68.23, 28.59, 26.85, 25.99. ESI-MS [M+H]+
calcd for C24H26N2O2: 374.1994, found: 375.2064. Analytical
Data. Found (calcd) for: C24H26N2O2 C, 76.98 (76.99); H, 7.00
(7.68); N, 7.48 (7.47).
8
9
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grant No. 21572155 and 21372175)
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Graphical Abstract
View Article Online
DOI: 10.1039/C8DT04290J
ROMP
n
ROMP
Yield : 93% Z/E : 98:2
+
R
or
ROCM
CM
ROCM
R
HO
OH
HO
OH
Yield : 73%-88%
CM
Z/E : 97:3-98:2
G
G
G
G/OH
+
or
Yield : 24%-52%
HO
OH
Z/E : 65:35-97:3
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