Efficient allylation of nucleophiles catalyzed by a bifunctional heterogeneous palladium complex-tertiary amine system

Article abstract of DOI:10.1002/adsc.201300063

We demonstrate the synergistic catalysis of a silica-supported diaminopalladium complex and a tertiary amine (SiO₂/diamine/Pd/ NEt₂) as well as synthetic scope of the Tsuji-Trost reaction of 1,3-dicarbonyls, phenols, and carboxylic acids with allyl carbonate and acetates. The synergistic catalysis of SiO₂/diamine/Pd/NEt ₂ exhibited wide applicability and high activity for the Tsuji-Trost reaction. For example, the reaction of ethyl 3-oxobutanate with allyl methyl carbonate afforded the allylated product in >99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO₂/diamine/Pd, without immobilization of the tertiary amine group. In the reaction of 1.0 mmol of ethyl 3-oxobutanate using 0.60 μmol of Pd in SiO₂/diamine/Pd/NEt ₂, the turnover number (TON) of Pd reached up to 1070 within 24 h. Phenols with electron-withdrawing groups, such as nitro and chloro groups, on the para position resulted in high product yields. The SiO₂/diamine/ Pd/NEt₂ catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of p-chlorophenol. Copyright

Full text of DOI:10.1002/adsc.201300063

FULL PAPERS
DOI: 10.1002/adsc.201300063
Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional
Heterogeneous Palladium Complex-Tertiary Amine System
a
a
a
a,
Hiroto Noda, Ken Motokura, Akimitsu Miyaji, and Toshihide Baba *
a
Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering,
Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8502, Japan
E-mail: tbaba@chemenv.titech.ac.jp
Received: January 23, 2013; Published online: March 19, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300063.
Abstract: We demonstrate the synergistic catalysis of tion of 1.0 mmol of ethyl 3-oxobutanate using
a silica-supported diaminopalladium complex and 0.60 mmol of Pd in SiO /diamine/Pd/NEt , the turn-
2
2
a tertiary amine (SiO /diamine/Pd/NEt ) as well as over number (TON) of Pd reached up to 1070 within
2
2
synthetic scope of the Tsuji–Trost reaction of 1,3-di- 24 h. Phenols with electron-withdrawing groups, such
carbonyls, phenols, and carboxylic acids with allyl as nitro and chloro groups, on the para position re-
carbonate and acetates. The synergistic catalysis of sulted in high product yields. The SiO /diamine/Pd/
2
SiO /diamine/Pd/NEt2 exhibited wide applicability NEt catalyst was reusable at least 4 times without
2
2
and high activity for the Tsuji–Trost reaction. For ex- appreciable loss of its activity and selectivity in the
ample, the reaction of ethyl 3-oxobutanate with allyl reaction of p-chlorophenol.
methyl carbonate afforded the allylated product in
>
99% yield at 708C for 5 h. The yield of allylated Keywords: 1,3-dicarbonyl compounds; palladium;
products was 26% for SiO /diamine/Pd, without im- phenols; synergistic catalysis; tertiary amines; Tsuji–
2
mobilization of the tertiary amine group. In the reac- Trost allylation
Introduction
catalyst is shown in Figure 1. Because of the anchor-
ing on the surface, it can be expected that the Pd
The Tsuji–Trost allylation of various nucleophiles cat- complex and amine in the SiO /diamine/Pd/NEt can
2
2
alyzed by Pd complexes is one of the most efficient exist together without significant mutual interaction.
protocols for CÀC and CÀO bond formation in organ- In the Tsuji–Trost reaction, the Pd complex activates
3
ic synthesis. The Tsuji–Trost reaction introduces an allyl methyl carbonate to form a h -allylpalladium
allyl group into an organic compound, which then has species while the tertiary amine simultaneously acti-
great potential for further elaboration. Various homo- vates ethyl 3-oxobutanate by abstraction of an a-
[1]
[2]
[4]
geneous and heterogeneous Pd catalysts have been proton (Scheme 1). This fact encouraged us to ex-
reported for the Tsuji–Trost reaction. amine various nucleophiles having acidic protons that
Synergistic catalysis of a Pd species and base has can be abstracted by the tertiary amine of the cata-
been reported in the Tsuji–Trost reaction in homoge- lyst.
[
3]
neous catalyst systems. The use of a base and
In this paper, we fully investigate the Pd-amine syn-
a Lewis acid metal center often results in self-quench- ergistic catalysis of the SiO /diamine/Pd/NEt system
2
2
ing, which renders both catalysts inactive. Thus, care-
ful selection of the appropriate base and Pd catalyst is
necessary for the acceleration of the Pd-catalyzed
[
3a]
Tsuji–Trost reaction with an amine base.
To overcome this problem, recently, we reported
preliminary results for heterogeneous synergistic cat-
alysis by a silica-supported diaminopalladium com-
plex and a tertiary amine (SiO /diamine/Pd/NEt ) for
2
2
the Tsuji–Trost reaction of ethyl 3-oxobutanate with
[
4]
allyl methyl carbonate. The surface structure of the Figure 1. Surface structure of SiO /diamine/Pd/NEt .
2
2
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Hiroto Noda et al.
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Scheme 1. Synergistic catalysis by SiO /diamine/Pd/NEt for the Tsuji–Trost reaction.
2
2
Scheme 2. The Tsuji–Trost reaction of 1,3-dicarbonyls, phenols, and carboxylic acids.
3
2
and its synthetic scope in the Tsuji–Trost reaction of the Q and Q site was observed after the immobiliza-
,3-dicarbonyls, phenols, and carboxylic acids tion of organic amine groups on the SiO surface
1
2
n
(
Scheme 2).
[Q =Si ACHTUNRTGNNEG(U OSi) (OH) ] (Figure S1 in the Supporting
n 4Àn
3 2
Information). Additionally, the T and T sites ap-
m
peared at À67 and À59 ppm, respectively [T =
2
9
Results and Discussion
RSi(OH)
ACHTUNGTNRENUNG( OSi) ], in the Si MAS NMR spectrum
Àm m
3
of SiO /diamine/Pd/NEt (Figure S1 in the Supporting
2
2
Scheme 3 represents the synthetic procedure of the Information). The presence of diaminopalladium and
(
A) SiO /diamine/Pd/NEt and (B) SiO /diamine/Pd. tertiary amine group in SiO /diamine/Pd/NEt , and di-
2
2
2
2
2
3
-(2-Aminoethylamino)propyltrimethoxysilane and 3- aminopalladium in SiO /diamine/Pd was determined
2
1
3
diethylaminopropyltrimethoxysilane were immobi- by solid-state C CP/MAS NMR measurement (Fig-
lized on the SiO surface using a silane-coupling reac- ure S2 in the Supporting Information). The XPS anal-
2
tion to give silica-supported amines (SiO /diamine/ ysis of Pd 3d5/2 showed a peak at 337.5 eV, which was
2
NEt ). SiO /diamine/Pd/NEt was prepared from assigned to the Pd(II) species (Figure S3 in the Sup-
2
2
2
SiO /diamine/NEt by treatment with a PdCl
A
H
U
G
R
N
N
porting Information).
2
2
2
solution in 2-propanol. SiO /diamine/Pd also was pre-
The Tsuji–Trost allylation of ethyl 3-oxobutanate
2
pared by a similar procedure, as shown in Scheme 3 (1) with allyl methyl carbonate (2) using the Pd cata-
B). The amounts of the immobilized amine and Pd lysts was examined. Results are shown in Table 1.
species were determined by elemental analysis. The SiO /diamine/Pd/NEt showed >99% yield of the
(
2
2
presence of carbon and nitrogen atoms suggests im- total allylated products (Table 1, entry 1), whereas the
mobilization of organic amines. A 1:2:2 Pd:Cl:N ratio yield of allylated products was 26% for SiO /diamine/
2
of the SiO /diamine/Pd indicates the presence of the Pd (Table 1, entry 2). The Tsuji–Trost reaction using
2
diamonopalladium chloride species, where the excess SiO /diamine/NEt did not proceed (Table 1, entry 3),
2
2
amount of N atoms in SiO /diamine/NEt indicates suggesting that the tertiary amine on SiO /diamine/
2
2
2
the presence of both diaminopalladium chloride spe- Pd/NEt2 accelerates Pd-catalyzed Tsuji–Trost reac-
cies and tertiary amine. The formation of covalent SiÀ tion. To examine the effect of immobilization of a ter-
OÀSiÀC bonds on the silica surface was confirmed by tiary amine on catalytic activity, reaction using SiO2/
29
solid-state Si MAS NMR measurement: decreases of diamine/Pd with a free tertiary amine (diethylbutyl-
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Adv. Synth. Catal. 2013, 355, 973 – 980

Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex
Scheme 3. Synthesis of (A) SiO /diamine/Pd/NEt and (B) SiO /diamine/Pd catalysts.
2
2
2
[a]
Table 1. Tsuji–Trost reaction using Pd catalysts.
[b]
[b]
[b]
Entry
Catalyst
Conversion of 1 [%]
Yield of 3 [%]
Yield of 4 [%]
1
2
3
4
5
SiO /diamine/Pd/NEt
>99
33
10
52
56
96
26
00
06
28
4
0
0
0
0
2
2
SiO /diamine/Pd
2
[c]
SiO /diamine/NEt
2
2
[d]
SiO /diamine/Pd+tertiary amine
2
SiO /diamine/Pd+SiO /NEt
2
2
2
[
a]
The data in this table were previously reported in ref.[4] Reaction conditions: 1 (1.0 mmol), 2 (2.5 mmol), K CO3
2
(
3.0 mmol), catalyst (Pd: 0.0060 mmol), THF (4.0 mL), 708C, 5 h.
[
[
[
b]
c]
d]
1
Determined by H NMR using internal standard technique. 1,3,5-Triisopropylbenzene was used as an internal standard.
0
0
.0128 g of SiO /diamine/NEt was used.
2
2
.01 mmol of diethylbutylamine was added.
ACHTUNGTRENNUNGa mine) was conducted (Table 1, entry 4). The amount with a free amine showed less activity (6% yield)
of the free tertiary amine used is similar to that in the than did SiO /diamine/Pd (Table 1, entry 4 vs. 2). Ad-
2
SiO /diamine/Pd/NEt . As a result, SiO /diamine/Pd ditionally, increasing the amount of the free tertiary
2
2
2
Adv. Synth. Catal. 2013, 355, 973 – 980
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Hiroto Noda et al.
FULL PAPERS
di-allylated products. Ranu et al. reported that the
mono-/di- ratio strongly depends on the solvent
[
5]
used. Table 2 summarizes the results of the reaction
between ethyl 3-oxobutanate (1) and allyl methyl car-
bonate (2) with SiO /diamine/Pd/NEt in various sol-
2
2
vents. Among the solvents examined, THF was found
to be the best solvent, affording 99% yield of allylat-
ed products with 93% selectivity of the mono-allylat-
ed one (3) (Table 2, entry 1). The major product using
DMF and ethanol was the di-allylated keto ester (4)
(
Table 2, entries 2 and 3). The yield of 3 was much
lower when using non-polar solvents (Table 2, en-
tries 6–8) than when polar solvents.
In the case of THF, the reaction completely
stopped after hot filtration of the catalyst at ca. 75%
[
4,6]
conversion.
This result indicates the reaction
occurs at the solid surface. However, in the case of
DMF, leaching of active Pd species into the homoge-
neous solution was detected. This suggests that the Pd
species at the solid surface showed high selectivity
toward the mono-allylated product in the Tsuji–Trost
reaction. Thus, THF was identified as the best solvent
Figure 2. Effect of additional free amine on the SiO /di-
ACHTUNGTRENNUNGa mine/Pd-catalyzed Tsuji–Trost reaction. Reaction condi-
2
tions: ethyl 3-oxobutanate (1) (1.0 mmol), allyl methyl car-
bonate (2) (2.5 mmol), K CO (3.0 mmol), SiO /diamine/Pd
for SiO /diamine/Pd/NEt -catalyzed Tsuji–Trost reac-
2
2
2
3
2
tion.
(
Pd: 0.0060 mmol), THF (4.0 mL), 708C, 5 h, free amine (di-
ethylbutylamine: 0–0.0098 mmol).
To investigate the synthetic applicability of the
SiO /diamine/Pd/NEt catalyst, we examined various
2
2
amine decreased product yield (Figure 2), indicating 1,3-dicarbonyls for the Tsuji–Trost reaction using
deactivation of the catalytic Pd site by the free terti- THF as a solvent, as shown in Table 3. In the reaction
ary amine. The product yield was not increased in the of several 1,3-dicarbonyls, the results for the SiO -sup-
2
case of physical mixture of SiO /NEt and SiO /di- ported Pd catalyst without a tertiary amine group
2
2
2
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
amine/Pd (Table 1, entry 5 vs. 2). Only a tertiary (SiO /diamine/Pd) are also shown. The reaction be-
2
amine immobilized on the same SiO surface can en- tween 1 and 2 with SiO /diamine/Pd/NEt proceeded
2
2
2
hance the Pd-catalyzed Tsuji–Trost reaction.
successfully (Table 3, entry 1). The reaction using
As mentioned above, the 1,3-dicarbonyl compound bulky keto esters having methyl, cyclic, and phenyl
having two active a-protons affords both mono- and groups proceeded with SiO /diamine/Pd/NEt , giving
2
2
[a]
Table 2. Reactions between ethyl 3-oxobutanate (1) and allyl methyl carbonate (2) in various solvents.
[b]
[c]
Entry
Solvent
Conversion [%]
Yield [%]
Mono-:Di-
1
2
3
4
THF
DMF
ethanol
acetonitrile
>99
>99
>99
52
>99
88
60
96:4
24:76
12:88
66:34
50
5
34
13
100:0
6
7
8
n-heptane
42
29
8
23
23
6
100:0
91:9
100:0
CH Cl
2
2
toluene
[
a]
Reaction conditions: 1 (1.0 mmol), 2 (2.5 mmol), K CO (3.0 mmol), SiO /diamine/Pd/NEt (Pd: 0.0060 mmol), solvent
2
3
2
2
(
4.0 mL), 708C, 5 h.
[
[
b]
c]
1
Determined by H NMR using internal standard technique. 1,3,5-Triisopropylbenzene was used as an internal standard.
The ratio of 3 and 4 was determined by integration of peaks in the H NMR spectra.
1
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Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex
[a]
Table 3. The Tsuji–Trost reaction of various 1,3-dicarbonyl compounds.
[
[
a]
b]
Reaction conditions: 1,3-dicarbonyl (1.0 mmol), 2 (2.5 mmol), K CO (3.0 mmol), catalyst
2
3
(
Pd: 0.0060 mmol), THF (4.0 mL), 708C.
1
Determined by H NMR using internal standard technique. 1,3,5-Triisopropylbenzene
was used as an internal standard.
[
[
[
[
c]
d]
e]
f]
Reuse experiment; reaction time: 7 h.
Isolated yield.
Reuse experiment; reaction time 15 h.
Reaction conditions: 1,3-dicarbonyl (3.0 mmol), 2 (7.5 mmol), K CO (9.0 mmol), catalyst
2
3
(
Pd: 0.0180 mmol), THF (12.0 mL), 708C.
61–71% yields of products (Table 3, entries 3–5). The examined the reuse experiments with two 1,3-dicar-
slightly lower product yields compared with nucleo- bonyl compounds, ethyl 2-oxobutanoate (entry 1) and
phile 1 indicate the difficulty in substrate access to dimethyl malonate (entry 7). The catalytic activity
the catalyst surface due to steric bulk. The SiO /di- slightly decreased in the 2nd use, however, prolonged
2
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
amine/Pd/NEt catalyst showed high activity for the reaction time allowed excellent yields.
2
reaction of a diester (Table 3, entry 7). The reaction
To reduce the amount of Pd in the Tsuji–Trost reac-
was also compatible with aliphatic (Table 3, entry 9), tion, the reaction of 1 and 2 was carried out using
aromatic (entry 11), and cyclic diketones (entries 12– 0.60 mmol of Pd in SiO /diamine/Pd/NEt ; the turn-
2
2
1
4). In all 1,3-dicarbonyls used for comparison, SiO2/ over number (TON) value reached up to 1070 within
diamine/Pd/NEt showed higher product yields than 24 h (Scheme 4).
SiO /diamine/Pd, a tertiary amine free catalyst. We
ACHTUNGTRENNUNG
2
2
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Hiroto Noda et al.
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Table 4. The Tsuji–Trost reaction of phenols and carboxylic
[a]
acids.
Scheme 4. Tsuji–Trost reaction using SiO /diamine/Pd/NEt
2
2
with a high TON value.
Scheme 5. The Tsuji–Trost reaction with allyl acetates.
The Tsuji–Trost reaction with allyl acetates instead
of allyl methyl carbonate was also examined using the
SiO /diamine/Pd/NEt catalyst. The results are shown
2
2
in Scheme 5. Both a simple allyl group and a methallyl
group can be introduced to 1 with allyl and methallyl
acetates, respectively.
[
[
a]
b]
To extend the scope of the SiO /diamine/Pd/NEt -
Reaction
conditions:
nucleophile
(1.0 mmol),
2
2
2
catalyzed Tsuji–Trost allylation, we next examined
the reaction of various phenols and carboxylic acids
with 2. The results are summarized in Table 4. Phenol
reacted with 1 to form allyl phenyl ether in 86% yield
using SiO /diamine/Pd/NEt (Table 4, entry 1), where-
(2.5 mmol), K CO (3.0 mmol), SiO /diamine/Pd/NEt2
2
3
2
(Pd: 0.020 mmol), THF (4.0 mL), 708C.
1
Determined by H NMR using internal standard tech-
nique. 1,3,5-Triisopropylbenzene was used as an internal
standard.
Isolated yield.
2
2
[c]
[d]
[e]
[f]
as the product yield using SiO /diamine/Pd was only
2
SiO /diamine/Pd was used as catalyst.
2
28%. These results indicate the synergistic catalysis of
2
3
4
nd use; reaction time: 15 h.
rd use; reaction time: 15 h.
th use; reaction time: 15 h.
the Pd complex and the tertiary amine in the etherifi-
cation of phenol. Electron-withdrawing groups, such
as nitro and chloro groups, on the para position of the
phenyl ring resulted in higher product yields (Table 4,
[
g]
entries 2 and 3) than phenol (entry 1) in a shorter re- a phenol with an electron-donating group will induce
action time. In contrast, electron-donating groups like an interaction of the phenol substrate with the Pd
methyl and methoxy groups led to diminished product complex, resulting in a relatively slow reaction rate.
yields (Table 4, entries 4 and 5). It has previously On the other hand, proton abstraction of phenols by
been reported that electron-withdrawing groups, such the amine enhances the nucleophilicity of the phenols
as nitro group, on the benzene ring significantly de- even with electron-withdrawing groups, which usually
[6]
crease the reactivity of phenol derivatives in the show low reactivity in the Tsuji–Trost reaction. The
[
7]
Tsuji–Trost reaction. In contrast, the SiO /diamine/ Tsuji–Trost reaction of carboxylic acids also proceed-
2
Pd/NEt catalyst showed higher activity in the case of ed with the SiO /diamine/Pd/NEt catalyst (Table 4,
2
2
2
an electron-withdrawing group compared to that of entries 6 and 7). SiO /diamine/Pd/NEt catalyst was
2
2
an electron-donating group. It can be expected that reusable at least 4 times without appreciable loss of
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Adv. Synth. Catal. 2013, 355, 973 – 980

Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex
its activity and selectivity in the reaction of p-chloro- Preparation of the SiO /diamine/NEt
2
2
phenol (Table 4, entry 3).
3
2
SiO was pretreated at 1208C for 3 h under vacuum. SiO2
Formation of h -allylpalladium species on SiO /dia-
2
(
0.64 g) was placed in a round-bottom flask and treated with
a toluene solution containing 3-(2-aminoethylamino)pro-
pyl(trimethoxy)silane (0.4 mmol) and 3-diethylaminopro-
mine/Pd/NEt catalyst was confirmed by solid-state
2
13
C CP/MAS NMR analysis: after treatment of SiO2/
diamine/Pd/NEt2 with allyl methyl carbonate and pyl(trimethoxy)silane (1.6 mmol) at 408C for 1 h. The tolu-
K CO , new signals appeared at d=68, 75, and ene was removed by vacuum evaporation.
2
3
13
1
06 ppm in the solid-state C CP/MAS NMR spec-
trum. Signals at around 70 and at 106 ppm correspond
to terminal and center carbon atoms, respectively, of
the h -allylpalladium species. To clarify the proton SiO /diamine/NEt was placed in a round-bottom flask and
abstraction from 1,3-dicarbonyls by the tertiary amine treated with a 2-propanol solution containing PdCl ACHTUNTGENNURNG( PhCN)
Preparation of the SiO /diamine/Pd/NEt
2
2
3
[8]
2
2
2 2
at 908C for 4 h. The resulting mixture was filtered and
group on the SiO surface, Michael reactions of 1 with
2
washed with 2-propanol and CH Cl .
methyl vinyl ketone were conducted using SiO /NEt .
2
2
2
2
As a result, a 27% yield of Michael adduct was ob-
tained with SiO /NEt within 5 h, whereas no product
2
2
Preparation of the SiO /diamine/Pd
2
formed with parent SiO . These results indicate the
2
2
SiO was pretreated at 1208C for 3 h under vacuum. SiO2
synergistic catalysis of surface Pd species and tertiary
amine group, as shown in Scheme 1.
(
0.64 g) was placed in a round-bottom flask and treated with
a toluene solution containing 3-(2-aminoethylamino)pro-
pyl(trimethoxy)silane (0.4 mmol) at 408C for 1 h. The tolu-
ene was removed by vacuum evaporation. The resulting
silica-supported diamine was placed in a round-bottom flask
and treated with a 2-propanol solution containing PdCl2
Conclusions
A silica-supported Pd complex and tertiary amine was
synthesized and characterized. The synergistic cataly- and washed with 2-propanol and CH Cl .
AHCTUNGTNERNU(G PhCN) at 908C for 4 h. The resulting mixture was filtered
2
2
2
sis was observed only when the surface contained
both immobilized Pd complex and tertiary amine. The
bifunctional heterogeneous catalyst have been found
to be an active and selective for the Tsuji–Trost allyla-
tion of various nucleophiles, such as 1,3-dicarbonyls,
General Procedure for the Tsuji–Trost Reaction of
,3-Dicarbonyl Compounds
1
Silica-supported Pd catalyst (Pd: 0.0060 mmol), THF
phenols, and carboxylic acids in THF solvent. The (4.0 mL), 1,3-dicarbonyls (1.0 mmol), allyl methyl carbonate
turnover number (TON) of Pd reached up to 1070 (2.5 mmol) and K
within 24 h. Allyl acetates could also be used as ally-
lating agents in place of allyl methyl carbonate.
CO (3.0 mmol) were placed in a Pyrex
2
3
glass reactor. The resulting mixture was vigorously stirred
for 5 h at 708C under argon. The products were confirmed
by GC-MS and NMR analyses of the reaction mixture.
1
Yield and conversion were determined by H NMR using
a CDCl solution of the reaction mixture. The resulting mix-
3
Experimental Section
ture was purified over a column of silica gel (C200) and
eluted with hexane/ethyl acetate to give the isolated prod-
uct.
General Remarks
In reuse experiments, new substrates were added to the
same reactor after the first run, due to the significant deacti-
vation of the catalyst during the simple filtration process
under air.
1
13
Proton ( H) and carbon ( C) nuclear magnetic resonance
NMR) spectra were recorded in CDCl with an AVANCE
4
(
3
00 spectrometer operating at 400 and 100.6 MHz, respec-
13 29
tively. Solid-state C and Si MAS NMR spectra (MAS
rate=5 kHz) were recorded with an AVANCE III spec-
trometer operated at 100.6 and 79.5 MHz, respectively.
Cross-polarization (CP) contact time of the C CP/MAS
NMR measurements was 1.0 ms. Accumulation number and
delay time were about 20,000 and 20 s, respectively for C,
and 10,000 and 15 s, respectively, for Si. Adamantane (d=
8.52 and 29.47 ppm) and hexamethylcyclotrisiloxane (d=
General Procedure for the Tsuji–Trost Reaction of
Phenols and Carboxylic Acids as Nucleophiles
1
3
1
3
Silica-supported Pd catalyst (Pd: 0.020 mmol), THF
(4.0 mL), nucleophile (1.0 mmol), allyl methyl carbonate
(2.5 mmol) and K CO (3.0 mmol) were placed in a Pyrex
2
9
3
2
3
À9.66 ppm) were used as external standards for the calibra-
glass reactor. The resulting mixture was vigorously stirred
for 5 h at 708C under argon. The products were confirmed
by GC-MS and NMR analyses of the reaction mixture.
tion of chemical shifts. Aerosil 300 was used as SiO . SiO
2
2
was treated at 1208C under vacuum before use. Unless oth-
erwise noted, all other materials were purchased from Wako
Pure Chemicals, Tokyo Kasei Co., Kanto Kagaku Co., and
Aldrich Inc. and were used without further purification.
1
Yield and conversion were determined by H NMR using
a CDCl solution of the reaction mixture. The resulting mix-
3
ture was purified over a column of silica gel (C200) and
eluted with hexane/ethyl acetate to give the isolated prod-
uct.
1,3,5-Triisopropylbenzene was used as an internal standard
in catalytic reactions.
Adv. Synth. Catal. 2013, 355, 973 – 980
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
979

Hiroto Noda et al.
FULL PAPERS
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ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 973 – 980