PEG-4000-promoted palladium-catalyzed N-allylation in water: Aminonaphthalene as an example

Article abstract of DOI:10.1002/aoc.2899

An environmentally friendly, efficient catalytic process using palladium associated with ligands in a PEG4000-water system leading to N-allylation was described in this study. PEG-4000 was found to improve the palladium-catalyzed allylic amination of allylic acetates with aminonaphthalenes and gave overall good to high yields of the corresponding N-allylic aminonaphthalenes. Copyright

Full text of DOI:10.1002/aoc.2899

Full Paper
Received: 24 April 2012
Revised: 29 May 2012
Accepted: 17 June 2012
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.2899
PEG-4000-promoted palladium-catalyzed
N-allylation in water: aminonaphthalene
as an example
Chun-Jen Shiha, Yi-Jen Shuea, Shiang-Yu Yangb and Shyh-Chyun Yanga*
An environmentally friendly, efficient catalytic process using palladium associated with ligands in a PEG4000–water system
leading to N-allylation was described in this study. PEG-4000 was found to improve the palladium-catalyzed allylic amination
of allylic acetates with aminonaphthalenes and gave overall good to high yields of the corresponding N-allylic aminonaphthalenes.
Copyright © 2012 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: palladium-catalyzed; allylation; water; aminonaphthalenes; allylic acetates; polyethylene glycols
salting-in or salting-out effects, or surfactants and cyclodextrins
Introduction
can be added, the pH can be varied, and co-solvents or biphasic
reaction systems can be utilized.[11a] Many successful applications
Allylamines are pivotal building blocks for various biological
properties and advanced intermediates in total synthesis of natural
products[1] and especially those involving ring-closing metathesis.[2]
Therefore their synthesis is still an important area of activity.
Palladium-catalyzed transformations of allylic compounds have
demonstrated powerful and well-established synthetic procedures
for carbon–carbon and carbon–heteroatom (N, O, S) bond forma-
tion.[3] With respect to the reaction mechanism, palladium-catalyzed
allylation proceeds via p-allyl palladium complexes.[4] Most of the
mechanistic studies focus on either the elimination of the leaving
group or the attack of the amine.[5]
Aromatic amines have not been used commonly in allylic
amination, presumably because they are less nucleophilic than
the more commonly used benzylamine or stabilized anionic
nitrogen nucleophiles.[6] In this paper, we chose 1-aminonaphthalene
as our lead compound, because not only is it the core of the photo-
induced electron donor but it was also developed to investigate the
electron injection and charge recombination processes in DNA
duplex.[7] 1-Aminonaphthalene is also widely used in the organic
chemical industry as an intermediate of dye and rubber antioxi-
dants.[8] Moreover, naphthylamine can be oxidized by chromic acid
into naphthoquinone, which is a fundamental ring structure related
to vitamin K.[9]
of the aqueous biphasic method have resulted from the use of
polyethylene glycol (PEG) as the polymeric support.[13]
PEG employed as soluble supports for biphasic reaction
systems must: (i) be commercially available or rapidly and
conveniently prepared; (ii) demonstrate good mechanical and
chemical stabilities; (iii) provide appropriate functional groups
for easy attachment of organic moieties; and (iv) exhibit high
solubilizing power in order to dissolve molecular entities with
low solubilities and permit the development of a general
synthetic methodology independent of the physicochemical
properties of target compounds.[13g] PEG is nontoxic and
nonvolatile as well as being miscible with water.[14] The use of
PEG has been reviewed as a green reaction medium in which
its phase-transfer properties and its applications in solutions with
water have been highlighted.[13b] It can be isolated by a simple
phase separation, if used with organic substrates in a biphasic
reaction system. As a logical extension of our previous work,[12]
we further find that the palladium-catalyzed N-allylation could
occur smoothly under a PEG–water system. We wish to present
herein the experimental results.
Results and Discussion
With green chemistry processes and concerns over the environ-
mental impacts of using volatile organic solvents, the promising
potentials of water and other non-conventional solvents have
become highly noteworthy in designing organic syntheses.[10]
Water is the cheapest, most abundant solvent available. It also
has the highest value for specific heat capacity, enabling more
facile control of an exothermic reaction, and has a network of
hydrogen bonds which can influence the reactivity of substrates.[11]
Palladium-catalyzed N-allylation in water had been developed in
our lab.[12] On the basis of our previous study, the reactions
needed under reflux conditions and reaction time of some
derivatives was more than an hour. Other interesting features of
water are that additives such as salts can be used, inducing
In a recent report, we treated a mixture of 1-aminonaphthalene
(1a) and allyl acetate (2a) in the presence of catalytic amounts
of Pd(OAc)2 and PPh3 in ’pure water’ under reflux condition for
*
Correspondence to: Shyh-Chyun Yang, School of Pharmacy, College of Pharmacy,
Kaohsiung Medical University, Kaohsiung 807, Taiwan. E-mail: scyang@kmu.edu.tw
a School of Pharmacy, College of Pharmacy, Kaohsiung Medical University,
Kaohsiung 807, Taiwan
b School of Medicine, College of Medicine, Kaohsiung Medical University,
Kaohsiung 807, Taiwan
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.

C.-J. Shih et al.
30 min, and overall product yield was 88% (Table 1, entry 1).[12]
The reaction temperature was reduced to 70ꢀC and the result
was found to be similar to entry 1 (entry 2). Nevertheless, we
treated another aminonaphthalene derivative under ’pure-water’
conditions to give lower yields. Moreover, the addition of
PEG-4000 led to a rapid increase of activity and tended to mono-
allylation of 1-aminonaphthalene in the aqueous media (entries
3–11). As far as we know, a number of palladium catalysts are
commercially available and their reactivity, stability and selectiv-
ity can be tuned by ligands and/or additives.[10a] Herein, we be-
lieve PEG was the appropriate additive for mono-selectivity. The
optimal ratio of PEG:water was 1.5:3 g (entry 5). The reaction
was perfectly stable in air and was carried out in the presence
of catalytic amounts of Pd(OAc)2 (0.02 mmol) and PPh3
(0.08 mmol) at 70ꢀC for 15 min. In addition, the effect of various
chain-length PEGs on the reaction was examined under the same
reaction conditions (entries 7–10). PEG-4000 was superior to all
other PEGs, and therefore PEG-4000 was used as the source of
PEG throughout the studies. High efficiency of the Pd(OAc)2–
H2O–PEG system is probably attributed to the properties of
PEG as co-solvent and phase transfer catalyst. The reaction at
room temperature gave only 3a in 37% yield (entry 11). As with
our observation, N-allylation of 1a may proceed to give the
monoallylation product 3a first, which is then allylated to give
diallyated 4a. Therefore, increasing the relative amount of
allyl acetate favored the formation of the diallylated 4a (entries
12 and 13).
It was confirmed that the reaction did not occur in the absence
of palladium species (Table 2, entry 1). The yields were only 19%
in the absence of phosphine ligand (entry 2). Among the
palladium catalysts were Pd(OAc)2 (entry 3), Pd(acac)2 (entry 4),
Pd(OCOCF3)2 (entry 5), Pd(propionate)2 (entry 6), PdCl2 (entry 7),
PdCl2(MeCN)2 (entry 8), PdCl2(PhCN)2 (entry 9), PdCl2(1,10-Phen)2
(entry 10), [Pd(allyl)Cl]2 (entry 11), Pd(hfacac)2 (entry 12), Pd(PPh3)4
(entries 13 and 14) and Pd2(dba)3 (entry 15). Pd(OAc)2, Pd(acac)2,
Pd(OCOCF3)2, Pd(propionate)2, PdCl2(MeCN)2, [Pd(allyl)Cl]2, Pd(hfacac)2
and Pd2(dba)3 were found to be superior. PdCl2 and PdCl2(1,10-Phen)2
decreased the yield of products (entries 7 and 10). However, using
phosphine-based Pd(0) complex Pd(PPh3)4 with extra PPh3 as
catalyst increased the product yields (entry 13). [Pd(allyl)Cl]2 has
been used in another aminonaphthalene derivative and gave lower
yields, although it was the most effective Pd catalyst in the reaction
of 1-aminonaphthalene with allyl acetate. Considering the above
Table 2. Palladium-catalyzed allylation of 1-aminonaphthalene (1a)
with allyl acetate (2a): palladium catalyst and phosphine ligand
effectsa
Entry
Pd catalyst
Ligand
Yield (%)b (3a:4a)
1
—
PPh3
—
0
2
Pd(OAc)2
19 (100:0)
94 (90:10)
92 (93:7)
88 (95:5)
87 (97:3)
1 (100:0)
84 (87:13)
79 (92:8)
25 (92:8)
99 (97:3)
86 (95:5)
78 (94:6)
84 (98:2)
86 (97:3)
85 (75:25)
88 (94:6)
91 (91:9)
97 (91:9)
75 (95:5)
84 (90:10)
81 (88:12)
86 (88:12)
9 (100:0)
84 (96:4)
87 (97:3)
80 (94:6)
15 (100:0)
3
Pd(OAc)2
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
4
Pd(acac)2
5
Pd(OCOCF3)2
Pd(propionate)2
PdCl2
6
Table 1. Palladium-catalyzed allylation of 1-aminonaphthalene (1a)
with allyl acetate (2a): polyethylene glycols effectsa
7
8
PdCl2(MeCN)2
PdCl2(PhCN)2
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
PdCl2(1,10-Phen)2 PPh3
[Pd(allyl)Cl]2
PPh3
PPh3
—
c
Pd(hfacac)2
Pd(PPh3)4
Pd(PPh3)4
Pd2(dba)3
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PPh3
PPh3
Entry
PEG species
PEG/water (w/w)
Yield (%)b (3a:4a)
(2-MeC6H4)3P
(3-MeC6H4)3P
(4-MeC6H4)3P
(2-pyridyl)Ph2P
(2-furyl)3P
1c
2
—
0/5
0/3
88 (73:27)[12]
84 (90:10)
89 (79:21)
87 (95:5)
—
3
PEG-4000
PEG-4000
PEG-4000
PEG-4000
PEG-600
PEG-1000
PEG-2000
PEG-6000
PEG-4000
PEG-4000
PEG-4000
0.5/3
1/3
4
5
1.5/3
2/3
94 (90:10)
94 (82:18)
81 (90:10)
80 (90:10)
79 (94:6)
(4-ClC6H4)3P
(4-FC6H4)3P
(4-MeOC6H4)3P
[2,6-(MeO)2C6H3]3P
(ꢁ)-BINAPd
Dppfe
6
7
1.5/3
1.5/3
1.5/3
1.5/3
1.5/3
1.5/3
1.5/3
8
9
10
11d
12e
13f
82 (98:2)
37 (100:0)
97 (68:32)
96 (5:95)
Dpphf
Dppbg
aReaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd catalyst
(0.015 mmol), ligand (0.08 mmol) and PEG-4000 (1.5 g) in water
(3 g) were reacted at 70ꢀC for 15 min.
bIsolated yield.
cPalladium hexafluoroacetylacetonate.
d(ꢁ)-2,20-Bis(diphenylphosphino)-1,10-binaphthyl.
eBis(diphenylphosphino)ferrocene.
f1,6-Bis(diphenylphosphino)hexane.
g1,4-Bis(diphenylphosphino)butane.
aReaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd(OAc)2
(0.02 mmol), and PPh3 (0.08 mmol) in PEG–water system were
reacted at 70ꢀC for 15 min.
bIsolated yield.
cReacted under reflux conditions for 30 min.
dReacted at room temperature.
eCompound 2a (1.2 mmol) was used.
fCompound 2a (4 mmol) was used.
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Appl. Organometal. Chem. (2012)

PEG-4000-promoted palladium-catalyzed N-allylation
Table 3. Reaction of aminonaphthalenes 1 with allyl acetates 2a
Entry
1
2
Product
Yields (%)b
2a
1
3b
4b
68
1b
20
2c
1b
1c
2a
2a
3b
4b
57
11
3
3c
4c
54
21
4
2a
3d
4d
76
1d
8
5d
2a
2a
2b
3e
3f
5
40
1e
6
78
28 (E/Z = 76/24)d
58
1f
7
1a
6
Appl. Organometal. Chem. (2012)
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C.-J. Shih et al.
Yields (%)b
32
Table 3. (Continued)
Entry
1
2
Product
2c
8
1a
7
8
64
9
Not obtained
2d
9
1a
10
81
11
12
13
17
2e
10
1a
80
2f
11
1a
71
aReaction conditions: 1 (1 mmol), 2 (0.8 mmol), Pd(OAc)2 (0.02 mmol), PPh3 (0.08 mmol) and PEG-4000 (1.5 g) in water (3 g) were reacted at 70ꢀC for
15 min.
bIsolated yield.
cWithout PEG-4000.
dReacted for 24 h.
eDetermined by GC.
and cost issues, Pd(OAc)2 has been employed as the palladium
source, and a screening of monodentate and bidentate phosphine
ligand has been undertaken. In the presence of various monodentate
ligands including (2-MeC6H4)3P, (3-MeC6H4)3P, (4-MeC6H4)3P,
(2-pyridyl)Ph2P, (2-furyl)3P, (4-ClC6H4)3P, (4-FC6H4)3P, (4-MeOC6H4)3P
and [2,6-(MeO)2C6H3]3P (entries 16–24), the results were satisfactory,
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Appl. Organometal. Chem. (2012)

PEG-4000-promoted palladium-catalyzed N-allylation
]except for [2,6-(MeO)2C6H3]3P (entry 24). Bidentate ligands
such as (ꢁ)-BINAP, dpph and dppf could give good yields
ranging from 80% to 87% (entries 25–27). Dppb afforded low yields
of products (entry 28). Except for (2-MeC6H4)3P (entry 16), satisfac-
tory selective results were obtained regardless of Pd catalysts or
ligands.
Finally, the above process was extended to different kinds of
aromatic amine (Scheme 1), providing additional versatility to
the reaction process. However, low yields (5% overall) were
found. We continued to increase the amount of catalyst system
and prolong the reaction time to improve the yield. Although this
gave a moderate yield and seemed less product selective, there is
potential for further study.
To explore the scope of this novel system, N-allylation of a
series of aminonaphthalenes with allyl acetates using Pd(OAc)2
and PPh3 in a PEG-4000–water system are summarized in Table 3.
Sterically demanding 1-amino-2-methylnaphthalene (1b) has
afforded monoallylated 3b and diallylated 4b in 68% and 20%
yields, respectively (entry 1). In the absence of PEG-4000, total
yields were decreased to 68% (entry 2). 2-Aminonaphthalene
(1c) gave mono- and diallylated products in 75% yield overall
(entry 3). The electron-deficient 1-amino-4-bromonaphthalene
(1d) delivered the N-allylated products 3d and 4d with high
yields (entry 4). Using aminonaphthalenes having strong
electron-withdrawing groups, such as the cyano group, under
reflux for 24 h, only the monoallylated product N-allyl-1-
(4-cyanonaphthyl)amine (3e) was obtained, but in low yield
(entry 5). It surprised us that the sterically more demanding
secondary N-ethyl-1-naphthylamine (1f) gave N-allyl-N-ethyl-1-
naphthylamine (3f) in 78% yield (entry 6). Encouraged by these
results, we studied the allylation of 1-aminonaphthalene (1a)
with both aliphatic and aromatic allyl acetates (Table 3, entries
7–11). Amination of 1-methylallyl acetate (2b) gave mixtures of
monoallylated 5 and regioisomeric 6 yields of 28% and 58%,
respectively (entry 7). These products may all be derived from
the same p-allyl intermediate, which can be attacked at either
the C-1 or C-3 position. The 76/24 E/Z ratio of 5 was determined
by gas chromatography (GC). Product E alkene arose from
the more thermodynamically stable syn p-allyl complex. 3,3-
Dimethylallyl acetate (2c) gave excellent yields of N-allylated
product 7 (32%) along with C-allylated product 8 (64%), which
was formed by aromatic amino-Claisen rearrangement of
regioisomer 9 (entry 8). In our previous paper, it was shown that
2c treated in ’pure water’ under reflux conditions gave only
moderate yields of 60%.[12] These findings show that PEGs
(i) demonstrate good mechanical and chemical stabilities, (ii)
provide appropriate functional groups for easy attachment of
organic moieties, and (iii) exhibit high solubilizing power in
order to dissolve molecular entities with low solubilities and
permit the development of a general synthetic methodology
independent of the physicochemical properties of target com-
pounds.[13g] The PEG-4000–water system was applicable to vari-
ous aromatic allyl acetates and tolerant to functional groups
such as methoxy and nitro groups. Both electron-rich and elec-
tron-withdrawing groups furnished good to excellent yields in
this reaction (entries 9–11).
Conclusion
The research has shown that palladium-catalyzed allylation of
aminonaphthalenes using allylic acetates in a PEG4000–water
system is a simple and efficient route for C–N bond formation. Both
selectivity toward mono-alkylated products and reaction yields are
improved. Moreover, this method is air-stable, economically viable
and environmentally friendly. The major advantages of the PEG-
4000–water system are three fold: all reactions are performed in
water; no additive other than PEG is required; and the temperature
of the reaction is usually lower than 100ꢀC. The products are obtained
in excellent yields and tended more to mono-substitution. Further
investigations on other applications are in progress.
Experimental
General
All new compounds were characterized by IR spectroscopy,
1H NMR, 13C NMR and GC-MS analysis. IR absorption spectra were
recorded on a PerkinElmer System 2000 FT-IR spectrophotometer.
Proton and 13C NMR were measured with a Unity-400 or Mercury
Plus-400 spectrometer. Carbon multiplicities were obtained from
distortionless enhancement by polarization transfer (DEPT) experi-
ments. Chemical shifts (d) and coupling constants (Hz) were mea-
sured with respect to TMS or chloroform-d1. Mass spectra and
high-resolution mass spectra were taken on a Thermo-Finnigan
trace gas chromatograph or Finnigan MAT-95XL instrument with
a direct inlet system.
General Procedure for the Palladium-Catalyzed Allylation of
Aminonaphthalenes
Reaction with 1-aminonaphthalene (1a): in a typical experiment,
a stirred mixture of 1-aminonaphthalene (1a) (143 mg, 1 mmol),
allyl acetate (2a) (81 mg, 0.8 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol),
PPh3 (21 mg, 0.08 mmol) and PEG-4000 (1.5 g) in water (3 g) was
heated to 70ꢀC for 15 min. After the mixture was cooled down
to room temperature, water and brine were added. The organic
materials were extracted with ether, dried over magnesium
sulfate and concentrated under vacuum. The crude product
was purified by column chromatography on silica gel with
chloroform–n-hexane (1:2) and afforded 3a (125 mg, 85%) and
4a (8 mg, 9%).
Compounds 3a,[15] 4a,[15] 3b,[15] 4b,[15] 3c,[15] 4c,[15] 3d,[15]
4d,[15] 3e,[15] 3f,[15] 5,[12] 6,[12] 7,[12] 8,[12] 10,[15] 11,[15] and 12[12]
are known.
NH2
OAc
N
NH
2a
+
Pd(OAc)2 (0.05 mmol)
PPh3 (0.2 mmol)
PEG-4000 (2 g)
H2O (3 mL)
Supporting Information
1g
3g 36%
4g 29%
70 oC, 1 h
Supporting information may be found in the online version of this
Scheme 1. Allylation of aniline (1g) with allylic acetate (2a)
article, including the data of compound 13.
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.
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C.-J. Shih et al.
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Acknowledgments
This work was supported by a grant from the National Science
Council of the Republic of China (NSC98-2119-M-037-001-MY3
and NSC101-2113-M-037-008-MY3). Chyi-Jia Wang and Min-Yuan
Hung (of the Center for Resources, Research and Development of
KMU) are thanked for analytic support.
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Appl. Organometal. Chem. (2012)

Full Paper
PEG-4000-promoted palladium-catalyzed N-allylation in water: aminonaphthalene as an
example
Chun-Jen Shih, Yi-Jen Shue, Shiang-Yu Yang and Shyh-Chyun Yang
R1
AcO
R2
Pd catalyst, ligand
PEG, H2O
NH2
R1
R1
R1
NH
+
N
+
R2
NH
R2
R2
R2
An eco-friendly method for C-N bond formation of allylic acetates using palladium associated with ligands in PEG-water
system leading to N-allylation was described.