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Simple palladium-catalyzed CЦN bond formation for poor nucleophilicity of aminonaphthalenes.

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Full Paper
Received: 21 September 2011
Revised: 25 October 2011
Accepted: 26 October 2011
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.1858
Simple palladium-catalyzed C–N bond
formation for poor nucleophilicity
of aminonaphthalenes
Yi-Jen Shue and Shyh-Chyun Yang*
Aromatic amines is not used commonly in allylic amination, presumably because of their less nucleophilic nature compared
with the more extensively used benzylamine or relatively stable anionic nitrogen nucleophiles. An eco-friendly method for
C–O bond activation of allylic acetates using palladium associated with ligands in water leading to N-allylation was described
in this study. The palladium-catalyzed allylic amination of allylic acetate with aminonaphthalenes gave 34–95% yields to the
corresponding N-allylic aminonaphthalenes. Copyright © 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: palladium-catalyzed; allylation; water; aminonaphthalenes; allylic acetates
Introduction
Appl. Organometal. Chem. 2011, 25, 883–890
Results and Discussion
We treated a mixture of 1-aminonaphthalene (1a, 1.5 mmol) and
allyl acetate (2a, 1.2 mmol) in the presence of catalytic amounts
of Pd(OAc)2 (0.015 mmol) and PPh3 (0.06 mmol) in water under room
temperature for 30 min. It was found that N-allyl-1-naphthylamine
(3a) and N,N-diallyl-1-naphthylamine (4a) were formed in yields of
only 26% and 10%, respectively (Scheme 2).
The reaction, under reflux, increased the yields of products 3a
and 4a to 64% and 24%, respectively (entry 1 in Table 1).
However, the yields were not increased when the reaction time
was prolonged to 1 h (entry 2). According to our observation,
the monoallylation process was faster than diallylation (entry 1).
Therefore, when product 4a was increased, the reaction may be
toward product 3a (entries 1 and 2). When trying to use a Pd:
PPh3 ratio of 1:2, the obtained yield was decreased to 7%.
Increasing the relative amount of allyl acetate favored the formation of the desired diallylated product 4a (entries 3 and 4). It was
confirmed that the yields were small in the absence of palladium
species (entry 5) or phosphine ligand (entry 6). Among the palladium catalysts, including Pd(OAc)2 (entry 1), Pd(acac)2 (entry 7),
PdCl2 (entry 8), Pd(OCOCF3)2 (entry 9), PdCl2(MeCN)2 (entry 10),
Pd(hfacac)2 (entry 11), [Pd(allyl)Cl]2 (entry 12), and Pd(PPh3)4
(entries 12 and 13), Pd(OAc)2, PdCl2, Pd(OCOCF3)2, PdCl2(MeCN)2,
Pd(hfacac)2, and [Pd(allyl)Cl2]2 were found to be superior. On the
* Correspondence to: Shyh-Chyun Yang, School of Pharmacy, College of Pharmacy,
Kaohsiung Medical University, Kaohsiung 807, Taiwan. E-mail: scyang@kmu.edu.tw
School of Pharmacy, College of Pharmacy, Kaohsiung Medical University,
Kaohsiung 807, Taiwan
Copyright © 2011 John Wiley & Sons, Ltd.
883
Allylamine is a pivotal compound because it functions as an intermediate in organic synthesis,[1] has biological properties,[2] and is
present extensively in various natural products.[3] Metal-catalyzed
transformation of allylic compounds has demonstrated powerful
and well-established synthetic procedures for C–C and C–N bond
formation.[4] Although many metal centers (Ni, Pd, Pt, Mo, W, Ir,
Ru)[4,5] have shown their capability to catalyze these transformations, most of the studies have merely focused on Pd(II) complexes, which are the proven most active and multi-functional
catalysts.[6] The catalytic cycle requires the formation of the
cationic Z3-allylpalladium(II) complex, which is an intermediate generated by oxidative addition of allylic compounds, including allylic halides,[4,7] esters,[8] and carbonates[9] to a Pd
complex and which can be attacked by nucleophiles at both
termini of the allylic system. The catalytic cycle is a widely
accepted presence in Scheme 1.[6] Most of the mechanistic
studies focus on either the elimination of the leaving group
or attack of the amine.[10]
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.[11] 1-Aminonaphthylene is the core of
the photo-induced electron donor, and it has been developed to
investigate electron injection and charge recombination processes
in the DNA duplex.[12] It is also widely used in the organic chemical
industry as an intermediate of dye and rubber antioxidants.[13]
Moreover, naphthylamine can be oxidized by chromic acid into
naphthoquinone, which is a fundamental ring structure related to
vitamin K.[14] With green chemistry processes and concerns over
the environmental impacts of using volatile organic solvents (VOCs),
the promising potential of water and other non-conventional
solvents has become highly noteworthy in designing organic
syntheses.[15] Water has become a highly recommended solvent
for organic reactions in terms of cost, safety, availability, and
environmental concerns.[16] Herein, we report an easy-to-achieve
protocol for the N-allylation of aminonaphthalenes with allylic
acetates using palladium complex in water.
Y.-J. Shue and S.-C. Yang
Table 1. Palladium-catalyzed allylation of 1-aminonaphthalene (1a)
with allyl acetate (2a)a
Scheme 1. Catalytic cycle of the nucleophilic allylic substitution
Scheme 2. Allylation of 1-aminonaphthalene (1a) with allyl acetate (2a)
884
basis of our observation, Pd(acac)2, which lowered the yield,
did not form any byproduct; therefore, it was determined that
the case was simply due to a low conversion ratio (entry 7).
However, using phosphine-based palladium complex Pd(PPh3)4
with extra PPh3 as catalyst increased the yield of products (entry
13). [Pd(allyl)Cl]2 has been used with another aminonaphthalene
derivative to give lower yield, although it was the most effective
Pd catalyst in the reaction of 1-aminonaphthalene with allyl
acetate. Considering the above-mentioned and cost issue, 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
PPh3, (2-MeC6H4)3P, (3-MeC6H4)3P, (4-MeC6H4)3P, (2-furyl)3P,
(2-pyridyl)Ph2P, and (4-ClC6H4)3P (entries 1 and 15–20), results
were satisfactory. Bidentate ligands such as dppp, dppb, dpph,
dppf, and ()-BINAP could give good yields, ranging from 81%
to 91% (entries 22–36).
To explore the scope of this novel system, N-allylation of a series
of aminonaphthalenes (1b–h) with allyl acetate (2a) using Pd(OAc)2
and PPh3 in water are summarized in Table 2. 2-Aminonaphthalene
(1b) has afforded mono- and diallylated products in good yields
(entry 1). When the relative amount of 2a was increased, the
selective diallylation product 4b could be obtained in 89% yield
(entry 2). 1-Amino-2-methylnaphthalene (1c) gave mono- and
diallylated products in 95% yield overall under reflux for 3 h
(entry 3). Using [Pd(allyl)Cl]2 for raising selectivity, however,
the effect was not obvious (entry 4). 1-Amino-4-bromonaphthalene
(1d) gave the N-allylated products in moderate yields (entry 5).
Using aminonaphthalenes having strong electron-withdrawing
groups, such as nitro group, under reflux for 24 hours, only the
monoallylated product N-allyl-1-(4-nitronaphthyl)amine (3e) was
obtained, however, in low yields (entry 6). These differences in reactivity could be related to the nucleophilicity of the corresponding
aminonaphthalenes. Treating heterocycle, such as 3-aminoquinoline
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Entry
Pd catalyst
Ligand
1
2c
3d
4e
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
—
Pd(OAc)2
Pd(acac)2
PdCl2
Pd(OCOCF3)2
PdCl2(MeCN)2
Pd(hfacac)2f
[Pd(allyl)Cl]2
Pd(PPh3)4
Pd(PPh3)4
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
PPh3
PPh3
PPh3
—
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
—
PPh3
(2-MeC6H4)3P
(3-MeC6H4)3P
(4-MeC6H4)3P
(2-pyridyl)Ph2P
(2-furyl)3P
(4-ClC6H4)3P
Dppeg
Dppph
Dppbi
Dpphj
Dppfk
()-BINAPl
Yield (%)b (3a:4a)
88 (73:27)
80 (93:7)
89 (25:75)
91 (3:97)
4 (100:0)
5 (100:0)
76 (89:11)
82 (79:21)
84 (88:12)
86 (88:12)
88 (94:6)
99 (97:3)
42 (86:14)
91 (97:3)
81 (83:17)
89 (75:25)
76 (97:3)
87 (89:11)
71 (94:6)
89 (87:13)
0
81 (95:5)
81 (95:5)
91 (76:24)
89 (97:3)
90 (91:9)
a
Reaction conditions: 1a (1.5 mmol), 2a (1.2 mmol), Pd catalyst
(0.015 mmol), and ligand (0.06 mmol) in water (5 ml) were refluxed
for 30 min.
b
Isolated yield.
c
Reflux for 1 h.
d
Compound 2a (3 mmol) was used.
e
Compound 2a (6 mmol) was used.
f
Palladium hexafluoroacetylacetonate.
g
1,2-Bis(diphenylphosphino)ethane.
h
1,3-Bis(diphenyIphosphino)propane.
i
1,4-Bis(diphenylphosphino)butane.
j
1,6-Bis(diphenylphosphino)hexane.
k
Bis(diphenylphosphino)ferrocene.
l
()-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl.
(1f), could also provide good result (entry 7). The structural features
of aminoquinoline involving proton donors, such as nitrogen
containing heterocyclic and amino groups, play an important
role in many biological and photochemical processes.[17] It
has surprised us that the sterically more demanding secondary
N-ethyl-1-naphthylamine (1g) gave N-allyl-N-ethyl-1-naphthylamine
(3g) 79% yield (entry 8). Phenothiazine (1h) that recent reports
employed to deal with promising anticancer, antibacterial, antiplasmid, multidrug resistance (MDR) reversal activities and as potential treatment in Alzheimer’s and Creutzfeldt-Jakob diseases[18]
reacted to give the corresponding N-allylamine in moderated
yields (entry 9).
The results for allylation of 1-aminonaphthalene (1a) with both
aromatic and aliphatic alcohols 2b–h in the presence of a
Copyright © 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 883–890
Palladium-catalyzed C-N bond formation
Table 2. Reaction of aromatic amines (1b–h) with allyl acetate (2a)a
Entry
1
h
1
Yield (%)b
Product
0.5
NH2
3b
54
4b
20
4b
3c
89
79
4c
16
3c
4c
3d
49
32
50
4d
3
3e
34
3f
38
4f
39
NH
1b
N
2c
3
1b
0.5
3
CH3
CH3
NH2
NH
1c
CH3
N
4d
1c
5
3
1.5
Br
Br
NH
NH2
1d
Br
N
6
NO2
24
NO2
NH
NH2
1e
7
1
N
N
NH
NH2
1f
8
N
N
885
Appl. Organometal. Chem. 2011, 25, 883–890
Copyright © 2011 John Wiley & Sons, Ltd.
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Y.-J. Shue and S.-C. Yang
Table 2. (Continued)
Entry
1
h
Yield (%)b
Product
2
3g
79
N
NH
1g
9
H
N
12
3h
66
N
S
1h
S
a
Reaction conditions: 1 (1.5 mmol), 2a (1.2 mmol), Pd(OAc)2 (0.015 mmol), and PPh3 (0.06 mmol) were refluxed in water (5 ml).
Isolated yield.
c
Compound 2a (3.3 mmol) was used.
d
[Pd(allyl)Cl]2 (0.015 mmol) was used.
b
catalytic amount of Pd(OAc)2 associated with PPh3 in water are
summarized in Table 3. Amination of 1-methylallyl acetate (2b)
gave mixtures of monoallylated, regioisomeric, and diallylated
aminonaphthalene 5, 6, 7, and 8 yields of 30%, 54%, 7%, and
3%, respectively (entry 1). 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. A 73:27 EE:EZ ratio of 7 was
determined by gas chromatography (GC). The stereochemistry
was confirmed by the coupling constant of the vinylic protons
for the major isomer (J = 15.2 Hz) as being characteristic of
E-stereochemistry. Product E alkene arose from the more
thermodynamically stable syn p-allyl complex. 3,3-Dimethylallyl
acetate (2c) gave monoallylated product 9 and 2-substituted
1-aminonaphthalene 10 in yields of 44% and 16%, respectively
(entry 2). The structure of compound 10 was determined by 1H
NMR and 2D NMR [heteronuclear multiple quantum correlation
(HMQC) and heteronuclear multiple bond correlation (HMBC)]. It was
found that there was no HMQC correlation with C-2 (d 120.0), and
the H-3 (d 7.23) and H-4 (d 7.28) had HMBC correlation with C-4a
(d 133.1) and C-8a (d 123.6). In addition, the H-3 (d 7.23), H-4
(d 7.28), and H-9 (d 3.41) all had HMBC correlation with C-1
(d 139.1). Amination of trans-2-hexen-1-yl acetate (2 d) gave
the allylating products 11 and 12 in moderate yields, but no
regioisomeric product was observed (entry 3). The reaction of
1-aminonaphthalene (1a) with aromatic allylic acetates 2e–h has
given good to high yields of products (entries 4–7). Both electronrich aryl groups and electron-withdrawing groups have furnished
good to excellent yields in this reaction (entries 5–7).
A possible mechanism for the formation of N-allylanilines from
1 and 2 is illustrated in Scheme 3, in which the substituent on
allylic acetate is omitted.19 Acetate 2 reacts with Pd(0) species
generated in situ to afford a p-allylpalladium intermediate (18).
Subsequently, the reaction of 18 with aminonaphthalene 1
followed by reductive elimination gives N-allylaminonaphthalene.
a simple and efficient route for C–N bond formation. Moreover,
this method is air stable, economically viable and environmentally friendly. The amination of allylic acetates worked well with
aminonaphthalenes and provided overall good to high yields of
the corresponding allylic aminonaphthalenes. Further investigations on other applications are in progress.
Experimental
General
Conclusion
886
In summary, the research has shown that palladium-catalyzed
allylation of aminonaphthalenes using allylic acetates in water is
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Scheme 3. Proposed mechanism
All new compounds were characterized by IR spectroscopy, 1H NMR, 13 C NMR, and GC-MS analysis. IR absorption
spectra were recorded on a PerkinElmer System 2000 FT-IR
Copyright © 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 883–890
Palladium-catalyzed C-N bond formation
Table 3. Reaction of 1-aminonaphthalene (1a) with allylic compounds (2b–h)a
Entry
2
Yield (%)b
Product
1
5
30
6
54 (E/Z = 86/14)c
7
7 (EE/EZ = 73/27)c
8
3
9
44
10
16
11
42
12
3
OAc
2b
NH
HN
N
N
2
OAc
2c
NH
4
3
4a
8a
2
1
9
NH2
3
OAc
2d
NH
N
887
Appl. Organometal. Chem. 2011, 25, 883–890
Copyright © 2011 John Wiley & Sons, Ltd.
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Y.-J. Shue and S.-C. Yang
Table 3. (Continued)
Entry
2
Yield (%)b
Product
OAc
4
d
13
2e
15
NH
14
74
15
77 (E/Z = 89/11)c
16
68
17
82
N
5d
OAc
H3CO
NH
2f
OCH3
6d
OAc
OCH3
NH
2g
OCH3
7d
OAc
O2N
NH
2h
NO2
a
Reaction conditions: 1a (1.5 mmol), 2 (1.2 mmol), Pd(OAc)2 (0.015 mmol), and PPh3 (0.06 mmol) in water (5 ml) were refluxed for 30 min.
Isolated yield.
c
Determined by GC.
d
Reflux for 3 h.
b
888
spectrophotometer. Proton and 13 C NMR were measured with
a Unity-400 or Mercury Plus-400 spectrometer. Carbon multiplicities were obtained from DEPT experiments. Chemical shifts
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(d) and coupling constants (Hz) were measured with respect to
tetramethylsilane or chloroform-d1. MS and high-resolution
mass spectra (HRMS) were taken on a Thermo-Finnigan to
Copyright © 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 883–890
Palladium-catalyzed C-N bond formation
trace GC or Finnigan MAT-95XL instrument, with a direct inlet
system.
General Procedure for the Palladium-Catalyzed Allylation of
Aminonaphthalenes
Appl. Organometal. Chem. 2011, 25, 883–890
Copyright © 2011 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc
889
Reaction with 1-aminonaphthalene (1a): in a typical experiment,
a mixture of 1a (215 mg, 1.5 mmol), allyl acetate (2a) (120 mg,
1.2 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), and PPh3 (16 mg,
0.06 mmol) in water (5 ml) was refluxed for 30 min. After the
mixture was cooled down to room temperature, water and
brine were added. The organic materials were extracted with
dichloromethane, 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 (134 mg, 61%) and 4a (32 mg, 24%).
Compounds 3a,[19] 4a,[19] 3b,[19] 4b,[19] 3c,[19] 4c,[19] 3 d,[19]
3e,[19] 3f,[19] 3 g,[19] 4 g,[19] 3 h,[19] 3i,[20] 11,[19] 12,[19] 13,[19] and
14[19] were synthesized according to the general procedure (for
reaction time see Tables 2 and 3).
Compounds 5–8: starting from 1-methylallyl acetate (2b)
(137 mg, 1.2 mmol) and following the general procedure,
monoallylated product 5 (71 mg, 30%), isomer 6 (128 mg,
54%), and diallylated products 7 (21 mg, 7%) and 8 (9 mg,
3%) were obtained.
N-(But-2E-enyl)-1-naphthylamine (5): brown oil. IR (KBr): n
3424 cm 1. 1H NMR (400 MHz, CDCl3): d 1.67 (t, J = 5.6 Hz, 3H, CH3),
3.71 (d, J = 5.6 Hz, 2H, CH2), 4.22 (bs, 1H, NH), 5.62–5.68 (m, 2H, vinyl
H), 6.54 (d, J = 7.6 Hz, 1H, ArH), 7.19 (d, J = 8.4 Hz, 1H, ArH), 7.29 (dd,
J = 7.6, 8.0 Hz, 1H, ArH), 7.32 (ddd, J = 1.6, 6.8, 8.4 Hz, 1H, ArH), 7.36
(ddd, J = 1.2, 6.8, 8.4 Hz, 1H, ArH), 7.68 (dd, J = 1.2, 8.4 Hz, 1H, ArH),
7.72 (dd, J = 1.2, 8.4 Hz, 1H, ArH). 13 C NMR (100 MHz, CDCl3):
d 17.7 (CH3), 46.1 (CH2), 104.6 (CH), 117.3 (CH), 119.8 (CH),
123.4 (C), 124.5 (CH), 125.5 (CH), 126.5 (CH), 127.6 (CH), 128.2
(CH), 128.5 (CH), 134.2 (C), 143.1 (C). EI-MS: m/z 197 (M+), 182,
168, 154, 143, 127, 115, 89, 77. EI-HRMS calcd for C14H15N:
197.1205, found: 197.1204.
N-(1-Methylallyl)-1-naphthylamine (6): brown oil. IR (KBr): n
3424 cm 1. 1H NMR (400 MHz, CDCl3): d 1.48 (d, J = 6.8 Hz, 3H,
CH3), 4.19 (dq, J = 6.4, 6.4 Hz, 1H, CH), 5.12 (ddd, J = 1.2, 1.2,
10.0 Hz, 1H, vinyl H), 5.24 (d, J = 17.2 Hz, 1H, vinyl H), 5.95 (ddd,
J = 6.0, 10.0, 17.2 Hz, 1H, vinyl H), 6.75 (bs, 1H, NH), 7.26–7.34
(m, 3H, ArH), 7.43–7.47 (m, 2H, ArH), 7.77–7.89 (m, 2H, ArH).
13
C NMR (100 MHz, CDCl3): d 21.7 (CH3), 51.3 (CH), 105.8 (CH),
114.4 (CH2), 117.3 (CH), 119.8 (CH), 123.4 (C), 124.6 (CH),
125.6 (CH), 126.5 (CH), 128.7 (CH), 134.4 (C), 140.9 (CH), 142.2
(C). EI-MS: m/z 197 (M+), 182, 168, 154, 143, 127, 115, 102, 89,
77. EI-HRMS calcd for C14H15N: 197.1204, found: 197.1204.
N,N-Di(but-2E-enyl)-1-naphthylamine (7): brown oil. 1H NMR
(400 MHz, CDCl3): d 1.63 (dd, J = 1.2, 6.0 Hz, 6H, CH3 2), 3.68
(d, J = 6.0 Hz, 4H, CH2 2), 5.48 (dtq, J = 1.2, 6.0, 15.2 Hz, 2H,
vinyl H), 5.59 (dtq, J = 1.2, 6.0, 15.2 Hz, 2H, vinyl H), 7.02 (d,
J = 7.6 Hz, 1H, ArH), 7.33 (dd, J = 7.6, 8.0 Hz, 1H, ArH), 7.38–7.46
(m, 2H, ArH), 7.48 (d, J = 8.4 Hz, 1H, ArH), 7.77 (dd, J = 1.6,
7.6 Hz, 1H, ArH), 8.28 (dd, J = 1.2, 8.0 Hz, 1H, ArH). 13 C NMR
(100 MHz, CDCl3): d 7.8 (CH3), 55.0 (CH2), 117.5 (CH), 122.9
(CH), 124.1 (CH), 125.0 (CH), 125.4 (CH), 125.5 (CH), 127.8
(CH), 128.0 (CH), 128.2 (CH), 130.0 (C), 134.8 (C), 148.0 (C).
EI-MS: m/z 251 (M+), 236, 222, 208, 196, 180, 168, 154, 141,
127, 115, 96, 77. EI-HRMS calcd for C18H21N: 251.1674, found:
251.1677.
N-(But-2E-enyl)-N-(1-methylallyl)-1-naphthylamine (8): deep-brown
oil. 1H NMR (400 MHz, CDCl3): d 1.14 (d, J = 6.4 Hz, 3H, CH3), 1.50 (dd,
J = 1.2, 6.4 Hz, 3H, CH3), 3.63–3.77 (m, 2H, CH2), 3.95 (dq, J = 5.6,
6.8 Hz, 1H, CH), 5.18 (dt, J = 1.6, 10.4 Hz, 1H, vinyl H), 5.22 (dt,
J = 1.2, 17.6 Hz, 1H, vinyl H), 5.35 (dtq, J = 1.2, 6.0, 15.2 Hz, 1H,
vinyl H), 5.50 (dtq, J = 1.2, 6.4, 15.2 Hz, 1H, vinyl H), 6.06 (ddd,
J = 5.2, 10.4, 17.6 Hz, 1H, vinyl H), 7.11 (d, J = 7.6 Hz, 1H, ArH),
7.37 (dd, J = 7.6, 8.0 Hz, 1H, ArH), 7.41–7.48 (m, 2H, ArH), 7.53
(d, J = 8.0 Hz, 1H, ArH), 7.80 (dd, J = 2.4, 6.4 Hz, 1H, ArH), 8.30
(dd, J = 2.4, 7.2 Hz, 1H, ArH). 13 C NMR (100 MHz, CDCl3): d 15.9
(CH3), 17.8 (CH3), 48.8 (CH2), 60.4 (CH), 115.0 (CH2), 119.8 (CH),
123.3 (CH),124.2 (CH), 125.1 (CH), 125.2 (CH), 125.5 (CH), 127.1
(CH), 128.2 (CH), 128.4 (CH), 131.5 (C), 134.9 (C), 140.7 (CH),
146.5 (C). EI-MS: m/z 251 (M+), 236, 222, 208, 196, 180, 168,
154, 141, 127, 115, 96, 77. EI-HRMS calcd for C18H21N:
251.1674, found: 251.1672.
Compounds 9 and 10: starting from 3-methylbut-2-enyl
acetate (2 d) (154 mg, 1.2 mmol) and following the general
procedure, monoallylated products 11 (112 mg, 44%) and 12
(41 mg, 16%) were obtained.
N-(3-Methylbut-2-enyl)-1-naphthylamine (9): deep-brown oil.
IR (KBr): n 3429 cm 1. 1H NMR (400 MHz, CDCl3): d 1.75 (s, 3H,
CH3), 1.80 (d, J = 1.2 Hz, 3H, CH3), 3.85 (d, J = 6.8 Hz, 2H, CH2), 4.20
(s, 1H, NH), 5.48 ( tq, J = 1.2, 6.8 Hz, 1H, vinyl H), 6.62 (d, J = 7.2 Hz,
1H, ArH), 7.24 (d, J = 8.0 Hz, 1H, ArH), 7.35 (dd, J = 7.6, 8.0 Hz, 1H,
ArH), 7.41 (ddd, J = 1.6, 6.8, 8.4 Hz, 1H, ArH), 7.44 (ddd, J = 1.6, 6.8,
8.4 Hz, 1H, ArH), 7.77–7.82 (m, 2H, ArH). 13 C NMR (100 MHz, CDCl3):
d 18.1 (CH3), 25.7 (CH3), 42.3 (CH2), 104.6 (CH), 117.4 (CH), 119.9
(CH), 121.3 (CH), 123.5 (C), 124.6 (CH), 125.7 (CH), 126.6 (CH), 128.6
(CH), 134.3 (C), 136.3 (C), 143.4 (C). EI-MS: m/z 211 (M+), 196, 180,
168, 154, 143, 127, 115, 89, 77. EI-HRMS calcd for C15H17N:
211.1361, found: 211.1361.
2-(3-Methylbut-2-enyl)-1-naphthylamine (10): reddish-brown
oil. IR (KBr): n 3382 cm 1. 1H NMR (400 MHz, CDCl3): d 1.77 (d,
J = 1.2 Hz, 3H, CH3), 1.81 (s, 3H, CH3), 3.41 (d, J = 6.8 Hz, 2H, CH2),
4.18 (s, 2H, NH2), 5.92 (tq, J = 1.2, 6.8 Hz, 1H, vinyl H), 7.23 (d,
J = 8.4 Hz, 1H, ArH), 7.28 (d, J = 8.4 Hz, 1H, ArH), 7.41 (ddd, J = 1.2,
6.8, 8.4 Hz, 1H, ArH), 7.42 (ddd, J = 1.6, 6.8, 8.4 Hz, 1H, ArH), 7.75
(dd, J = 1.2, 6.8 Hz, 1H, ArH), 7.77 (dd, J = 1.6, 6.8 Hz, 1H, ArH). 13 C
NMR (100 MHz, CDCl3): d 17.9 (CH3), 25.7 (CH3), 31.3 (CH2), 118.4
(CH), 120.0 (C), 120.2 (CH), 122.0 (CH), 123.6 (C), 124.8 (CH), 124.9
(CH), 128.5 (CH), 128.5 (CH), 133.1 (C), 133.5 (C), 139.1 (C). EI-MS:
m/z 211 (M+), 196, 179, 168, 156, 143, 129, 115, 89, 77. EI-HRMS calcd
for C15H17N: 211.1361, found: 211.1360.
N-[3-(4-Methoxyphenyl)allyl]-1-naphthylamine (15): following
the general procedure, the reaction of 1a (215 mg, 1.5 mmol),
3-(4-methoxyphenyl)allyl acetate (2 g) (247 mg, 1.2 mmol), Pd
(OAc)2 (3.4 mg, 0.015 mmol), and PPh3 (16 mg, 0.06 mmol) in
water (5 ml) was refluxed for 3 h to afford 16 (267 mg, 77%)
(eluent for chromatography: hexane–chloroform, 1:1): deep-brown
oil was isolated. IR (KBr): n 3421 cm 1. 1H NMR (400 MHz, CDCl3):
d 3.78 (s, 3H, CH3), 4.04 (dd, J = 1.2, 6.0 Hz, 2H, CH2), 4.49 (bs, 1H, NH),
6.28 (dt, J = 6.0, 16.0 Hz, 1H, vinyl H), 6.62 (d, J = 16.0 Hz, 1H, vinyl H),
6.66 (dd, J = 0.8, 7.6 Hz, 1H, ArH), 6.84 (d, J = 8.8 Hz, 2H, ArH), 7.24 (d,
J = 8.4 Hz, 1H, ArH), 7.31 (d, J = 8.8 Hz, 2H, ArH), 7.35 (d, J = 8.0 Hz, 1H,
ArH), 7.41 (ddd, J = 1.6, 6.8, 9.6 Hz, 1H, ArH), 7.44 (ddd, J = 1.6, 6.8,
9.6 Hz, 1H, ArH), 7.77–7.82 (m, 2H, ArH). 13 C NMR (100 MHz, CDCl3):
d 46.7 (CH3), 55.5 (CH2), 105.0 (CH), 114.2 (CH), 117.8 (CH), 120.1 (CH),
123.7 (C), 124.4 (CH), 124.9 (CH), 125.9 (CH), 126.8 (CH), 127.7 (CH),
128.9 (CH), 129.7 (C), 131.7 (CH), 134.5 (C), 143.4 (C), 159.4 (C).
EI-MS: m/z 289 (M+), 272, 242, 215, 180, 168, 147, 115, 91, 78. EI-HRMS
calcd for C20H19NO: 289.1467, found: 289.1464.
Y.-J. Shue and S.-C. Yang
N-[3-(2-Methoxyphenyl)allyl]-1-naphthylamine (16): following
the general procedure, the reaction of 1a (215 mg, 1.5 mmol),
3-(2-methoxyphenyl)allyl acetate (2 h) (247 mg, 1.2 mmol), Pd
(OAc)2 (3.4 mg, 0.015 mmol), and PPh3 (16 mg, 0.06 mmol) in
water (5 mL) was refluxed for 3 h and afforded 17 (236 mg,
68%) (eluent for chromatography: hexane–chloroform, 2:1):
deep-brown oil. IR (KBr): n 3432 cm 1. 1H NMR (400 MHz, CDCl3):
d 3.82 (s, 3H, CH3), 4.09 (dd, J = 1.2, 6.0 Hz, 2H, CH2), 4.56 (bs, 1H,
NH), 6.46 (dt, J = 6.0, 16.0 Hz, 1H, vinyl H), 6.68 (dd, J = 0.8,
7.6 Hz, 1H, ArH), 6.86 (dd, J = 1.2, 8.4 Hz, 1H, ArH), 6.92 (dt,
J = 0.8, 7.6 Hz, 1H, ArH), 7.03 (d, J = 16.0 Hz, 1H, vinyl H), 7.21
(dd, J = 1.6, 5.6 Hz, 1H, ArH), 7.25 (d, J = 5.6 Hz, 1H, ArH), 7.35
(t, J = 7.6 Hz, 1H, ArH), 7.41 (dt, J = 1.6, 7.2 Hz, 1H, ArH), 7.42 (t,
J = 2.4 Hz, 1H, ArH), 7.45 (dd, J = 1.6, 7.2 Hz, 1H, ArH), 7.78 (dd,
J = 2.4, 7.6 Hz, 1H, ArH), 7.82 (dd, J = 0.8, 7.2 Hz, 1H, ArH). 13 C
NMR (100 MHz, CDCl3): d 47.2 (CH3), 55.6 (CH2), 105.1 (CH),
111.0 (CH), 117.8 (CH), 120.2 (CH), 120.9 (CH), 123.7 (C), 124.9
(CH), 125.9 (CH), 126.0 (C), 126.8 (CH), 127.2 (CH), 127.4 (CH),
127.5 (CH), 128.8 (CH), 128.9 (CH), 134.5 (C), 143.4 (C), 156.8
(C). EI-MS: m/z 289 (M+), 168, 147, 115, 91, 77. EI-HRMS calcd
for C20H19NO: 289.1467, found: 289.1464.
N-[3-(4-Nitrophenyl)allyl]-1-naphthylamine (17): following the
general procedure, the reaction of 1a (215 mg, 1.5 mmol), 3-(4nitrophenyl)allyl acetate (2i) (265 mg, 1.2 mmol), Pd(OAc)2
(3.4 mg, 0.015 mmol), and PPh3 (16 mg, 0.06 mmol) in water
(5 mL) was refluxed for 3 h and afforded 18 (299 mg, 82%) (eluent
for chromatography: hexane–chloroform, 1:1): reddish-brown
crystal, m.p 131–132 C (chloroform–hexane). IR (KBr): n
3419 cm 1. 1H NMR (400 MHz, CDCl3): d 4.21 (dd, J = 0.8, 4.8 Hz,
2H, CH2), 4.72 (bs, 1H, NH), 6.63 (dt, J = 5.2, 15.6 Hz, 1H, vinyl H),
6.66 (dd, J = 1.6, 7.2 Hz, 1H, ArH), 6.76 (d, J = 15.6 Hz, 1H, vinyl H),
7.29 (d, J = 8.0 Hz, 1H, ArH), 7.36 (t, J = 8.0 Hz, 1H, ArH), 7.47 (d,
J = 8.4 Hz, 2H, ArH), 7.51 (d, J = 8.4 Hz, 2H, ArH), 7.81–7.87 (m, 2H,
ArH), 8.18 (d, J = 8.8 Hz, 2H, ArH). 13 C NMR (100 MHz, CDCl3):
d 46.1 (CH2), 104.9 (CH), 118.0 (CH), 119.7 (CH), 123.4 (C), 124.0
(CH), 124.9 (CH), 125.9 (CH), 126.5 (CH), 126.9 (CH), 128.8 (CH),
129.4 (CH), 132.0 (CH), 134.3 (C), 142.7 (C), 143.3 (C), 146.9 (C).
EI-MS: m/z 304 (M+), 287, 270, 257, 241, 215, 180, 167, 154, 141,
127, 115, 89, 77. EI-HRMS calcd for C19H16N2O2: 304.1212, found:
304.1209.
Supporting information
Supporting information may be found in the online version of
this article.
Acknowledgments
This work was supported by a grant from the National Science
Council of the Republic of China (NSC98-2119-M-037-001-MY3).
Chyi-Jia Wang and Min-Yuan Hung are thanked for analytical
support.
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Appl. Organometal. Chem. 2011, 25, 883–890
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