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Electronic Supplementary Material (ESI) for ChemComm.
This journal is © The Royal Society of Chemistry 2014
Role of Grafted Alkoxybenzylidene Ligand in Silica-Supported HoveydaGrubbs-Type Catalysts
Jian Liang Cheong, Daniel Wong, Song-Gil Lee, Jaehong Lim,* Su Seong Lee*
Institute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos, Singapore
138669
*E-mail: [email protected], [email protected]; Fax: (+65) 6478-9082.
Table of Contents
Experimental Procedure
S2
Scheme S1 Synthesis of MCF-supported DMT
S3
Fig. S1 CPMAS 13C NMR spectra of MCF-supported alkoxybenzylidene ligands
S5
recovered from the packed bed of the system b after one round of catalytic reaction
Fig. S2 Conversion of diethyl diallylmalonate by MCF-supported catalysts with
S6
different catalyst loading amount
Fig. S3 Conversion of diethyl diallylmalonate in the presence of MCF-supported DMT
S7
Fig. S4 CP-MAS NMR spectra
S8
S1
General
All reactions were carried out in oven-dried glassware under an inert atmosphere of dry argon.
All chemicals used were obtained from Aldrich or Alfa Aesar and used as received. All
MCF-supproted catalysts were prepared according to the previous report.1 An isocratic pump
from Agilent (1100 series G13104 with a control module) and a degasser from Waters (InLine Degasser AF, 4 Channels) were used for the circulating flow-type reactions.
13C
CP-
MAS and 29Si CP-MAS NMR spectra were recorded on a 400 MHz Bruker spectrometer for
the supported catalysts. GC analyses were conducted with an Agilent 7890A instrument
equipped with an HP-5 column. ICP-MS was performed on a Perkin Elmer DRC II ELAN
ICP-MS.
Preparation of packed beds
A stainless steel column (4.6 mm × 50 mm, Alltech) was filled with MCF-supported
metathesis catalysts (Catalyst loading: 0.2 mmol/g, 210 mg, 42 μmol) eluting with DCM at
high pressure (8000 psi) by using a slurry packer. By using the above procedure, MCFsupported Hoveyda-type ligands (ligand loading: 0.25 mmol/g, 110 mg, 27.5 μmol) were
packed into a stainless steel column (4.6 mm × 30 mm, Alltech) eluting with DCM. The
prepared packed beds were dried under high vacuum before use.
Catalytic reactions under ciculating flow conditions
The column was fitted into a solvent delivery system as shown in figure 1 and set to a desired
temperature by a column heater. Diethyl diallylmalonate (504.6 mg, 0.15 M) and dodecane
(178.8 mg, 0.075M) in DCM (14 ml) was circulateded at a flow rate of 0.5 ml/min. An
aliquot was taken from the outlet of the column, and the conversion at each time point was
measured by GC. After completion of the catalytic reation, the reaction solution was
collected from the outlet of the column, and the whole line with the reservoir flask was
completely washed with DCM. The washings were combined with the product solution. The
combined solutin was evaporated and dried for ICP-MS analysis.
Ring-closing metathesis reaction in a batch reactor
Diethyl diallylmalonate (144.2 mg, 0.05 M) and dodecane (51.1 mg, 0.025M) were added to
MCF-supported catalysts (catalyst d, 60 mg, 0.012 mmol, 2 mol%) in DCM (12 ml) at room
S2
temperature. During the catalystic reaction, an aliquot (200 l) was taken from the reaction
solution, filtered and then quenched with methanol. The conversion at each time point was
measured by GC. The same procedure was applied to cataly e and f.
Si
Si
OH
OH
OH
OH
OH
OH
OH
O
a
MCF
H2N
O
OH
Si
Si
O
O
b
OH
N
N
Cl
N
N
N
HN
d
O
Si
Si
Si
Si
Si
Si
Si
Si
Si
O
O
O
O
O
O
O
O
O
c
Cl
OH
H2N
H2N
MCF
Cl
OH
MCF
H2N
Si
Si
O
OH
OH
MCF
HS
Cl
N
N
S-Na+
N
HS
N
N
HN
HN
S-Na+
N
N
HN
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
O
O
O
O
O
O
O
O
O
O
O
O
O
O
e
MCF
MCF
Scheme S1. Synthesis of MCF-supported DMT. a. Hexamethylsilazane (HMDS), toluene; b.
APTES, toluene; c. HMDS, vapor-phase reaction; d. Cyanuric chloride, triethylamine,
anhydrous THF; e. NaSH, anhydrous ethanol.
Synthesis of MCF-supported dimercaptotriazine (DMT) as metal scavenger
MCF-supported DMT was synthesized according to scheme S1. MCF (3.0 g) was degassed at
120 °C overnight under vacuum before reaction. HMDS (253 mL, 1.2 mmol) was added to a
suspension of MCF in toluene (20 mL). The mixture was stirred at room temperature under
argon for 5 h, and then heated at 60 °C overnight. The resulting suspension was filtered,
washed with methanol, and then dried under vacuum. The resulting TMS-capped MCF (5.0 g)
was degassed at 120 C overnight under vacuum before reaction and then dispersed in
anhydrous toluene (30 ml). 3-aminopropyltriethoxysilane (APTES) (464 mg, 2.10 mmol) was
added to the mixture. The mixture was stirred at room temperature under argon for 3 h, and
then heated at 90 C overnight. The mixture was cooled down, filtered and washed with
toluene, CH2Cl2, and methanol. The collected particles were dried under vacuum. The NMR
spectrum of the filtrate after solvent evaporation confirmed the immobilization of all APTES.
S3
The particles were post-capped with TMS by the vapor-phase reaction with HMDS.
Elemental analysis, C:7.41, H:1.75, N:0.55. The calculated loading amount of NH2 on MCF
is 0.40 mmol/g.
A little bit excess of cyanuric acid (221 mg, 1.2 mmol, 1.5 eq) in 2 ml of THF was
slowly added to the resulting amine-functionalized MCF (2 g, 0.8 mmol of -NH2) in THF (8
ml), and then triethylamine (223 l, 1.6 mmol) in 2 ml of THF was added to the mixture
solution. After overnight reaction at room temperature, the MCF particles were recovered
through filtering, completely washed with anhydrous THF and dried in vacuum. The dried
MCF particles were reacted with NaSH (134 mg, 2.4 mmol) in anhydrous ethanol (10 ml) for
6hr and then recovered by filtration. The recovered MCF particles were completely washed
with ethanol and water, and then dried under vacuum to yield MCF-supported DMT
scavenger. The calculated loading amount of DMT on MCF is 0.38 mmol/g.
MCF-supported dichlorotriazine, Elemental analysis, C:8.70. H:1.72, N:2.12.
MCF-supported DMT, Elemental analysis, C:8.80, H:1.73, N:2.15, S:2.42.
References
1. (a) J. Lim, S. S. Lee and J. Y. Ying, Chem. Commun. 2010, 46, 806-808. (b) J.-E. Jee, J. L.
Cheong, J. Lim, C. Chen, S. H. Hong and S. S. Lee, J. Org. Chem. 2013, 78, 3048-3056.
S4
Fig. S1 CPMAS 13C NMR spectra of (a) MCF-supported alkoxybenzylidene ligands
recovered from the ligand bed B of the system b after one round of the flow reaction at 25 C,
(b) MCF-supported Hoveyda-Grubbs-type catalyst (3), and (c) MCF-supported
alkoxybenzylidene ligand (4). Red arrows indicate the presence of the ruthenium complexes.
S5
Fig. S1 Conversion of diethyl diallylmalonate by MCF-supported catalysts with different
catalyst loading amount. Conditions: catalyst (2 mol%), diethyl diallylmalonate (144.2 mg,
0.05 M), dodecane (51.1 mg, 0.025M), DCM (12 ml), 25 C.
100
Conversion (%)
80
60
0.12 mmol/g
0.20 mmol/g
0.32 mmol/g
40
20
0
0
50
100
Time (min)
S6
150
200
Fig. S2 Conversion of diethyl diallylmalonate in the presence of MCF-supported DMT.
Conditions: catalyst d (60 mg, 2 mol%), MCF-DMT (150 mg), diethyl diallylmalonate (144.2
mg, 0.05 M), dodecane (51.1 mg, 0.025M), DCM (12 ml), 25 C.
100
Conversion (%)
80
60
40
20
0
0
5
10
15
20
Time (hr)
S7
25
30
35
O
O
250
N
N N
200
150
S8
100
50
0.95
9.31
24.12
20.78
51.07
62.82
71.56
153.36
150.22
144.59
132.28
129.95
122.00
116.22
112.13
Fig. S3 CP-MAS NMR spectra.
Si
Si SiO2
EtO
Si
4
0
ppm
Cl
N
a
Ru
1.06
9.46
18.89
50.92
62.78
73.96
111.60
Si
b
Cl
O
SuSeong_0307_2013_C13_CP
2
O
1
G:\NMRuser
N
Si SiO2
EtO
sslee
Si
N N
3
60
80
[ *1e6]
128.43
153.81
145.93
138.06
213.19
247.69
257.27
N
Spinning rate = 10k Hz
a
20
40
b
0
Spiningn rate = 12k Hz
300
280
260
250
240
220
200
200
180 [ppm]
150
100
S9
50
0
ppm
0.56
9.27
19.54
50.51
62.23
73.65
111.38
128.23
153.12
145.56
137.79
System a
MCF-supported metathesis catalyst (A) recovered after one cycle
250
200
150
S10
100
50
0
ppm
0.74
9.12
19.96
50.83
73.93
71.18
62.51
128.58
121.41
115.50
111.96
153.06
145.84
138.12
System b
MCF-supported metathesis catalyst (A) recovered after one cycle
250
200
150
100
S11
50
0
ppm
1.28
9.71
20.60
51.25
74.37
71.62
62.72
153.68
150.49
145.17
138.46
129.17
122.42
116.01
112.18
System b
MCF-supported bidentate benzylidene ether ligand (B) recovered after one cycle
250
200
150
S12
100
50
0
ppm
1.12
9.84
20.32
51.24
62.66
71.60
112.16
129.03
122.01
153.58
146.26
138.49
System c
MCF-supported metathesis catalyst (A) recovered after one cycle
250
200
150
S13
100
50
0
ppm
0.99
9.75
20.57
51.28
62.71
71.55
153.59
150.33
144.83
138.59
132.28
129.48
121.94
116.17
112.14
System c
MCF-supported bidentate benzylidene ether ligand (B) recovered after one cycle
250
200
150
100
S14
50
0
ppm
:
250
O
200
O
N
N N
:
Cl
N
Cl
150
S15
N
Ru
Catalyst 5
100
50
0
ppm
0.98
9.57
20.29
29.72
51.08
74.13
71.31
62.62
153.36
150.02
145.41
138.20
131.90
128.90
121.49
115.41
111.76
0.97
17.37
10.71
26.07
50.29
44.31
60.15
Si
H 2N
Si SiO2
EtO
Si
250
200
150
100
S16
50
0
ppm
+
Na-S
N
N
N
Si
N
H
HS
250
Si SiO2
EtO
Si
200
150
100
S17
50
0
ppm
0.85
23.69
17.07
11.32
50.63
42.54
59.96
151.35
173.37
165.72
161.22
184.03
-99.86
-108.09
-56.16
-64.72
14.55
Si
O
O
N
N N
Si SiO2
EtO
Si
4
100
50
0
-50
S18
-100
-150
ppm
Cl
N
a
Ru
-99.69
-108.10
-55.97
-64.35
14.65
N
Si
b
Cl
O
O
N
N N
Si SiO2
EtO
Si
3
100
50
0
-50
S19
-100
-150
ppm
-99.67
-107.75
-64.95
-55.82
14.67
System a
MCF-supported metathesis catalyst (A) recovered after one cycle
100
50
0
-50
S20
-100
-150
ppm
-99.70
-108.53
-56.79
-64.95
13.88
Si
H 2N
Si SiO2
EtO
Si
100
50
0
-50
S21
-100
-150
ppm
+
Na-S
Si
N
N
N
HS
N
H
Si SiO2
EtO
Si
S22