Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water

Article abstract of DOI:10.1016/j.tet.2006.02.035

The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of anilines using allylic alcohols directly gave allylic anilines in good yields.

Full text of DOI:10.1016/j.tet.2006.02.035

Tetrahedron 62 (2006) 3949–3958
Direct palladium/carboxylic acid-catalyzed allylation
of anilines with allylic alcohols in water
*
Shyh-Chyun Yang, Yi-Chun Hsu and Kim-Hong Gan
Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University, Kaohsiung 807, Taiwan, ROC
Received 2 November 2005; revised 13 February 2006; accepted 14 February 2006
Available online 9 March 2006
Abstract—The direct activation of C–O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been
accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of anilines using allylic
alcohols directly gave allylic anilines in good yields.
q 2006 Elsevier Ltd. All rights reserved.
1. Introduction
conversion of allylic alcohols directly into allylation
products are highly desirable, especially from the viewpoint
of the atom economy.10 For achieving the palladium-
catalyzed C–O bond cleavage of allylic alcohols, various
other processes to facilitate the bond cleavage have been
reported.11 These processes include conversion of allylic
alcohols into the esters of inorganic acids (e.g., As2O3,12
B2O3,13 CO23b) or employment of a Lewis acid (e.g.,
BEt3,14 BF3,15 BPh3,16 SnCl217). However, there have been
only limited and sporadic reports dealing with the direct
cleavage of the C–O bond in allylic alcohols on interaction
with a transition metal complex.18 Successful applications
using allylic alcohols directly in catalytic processes are even
more limited. This apparently stems from the poor
capability of a nonactivated hydroxyl to serve as a leaving
group.16 Ozawa reported that (p-allyl)palladium complexes
bearing diphosphinidenecyclobutene ligands effectively
catalyze the direct conversion of allylic alcohols in the
absence of activating agents.19 Manabe20 in 2003 and Patil21
in 2004 disclosed the direct palladium-catalyzed allylic
substitution of allylic alcohols by carbon nucleophiles. We
have recently reported our attempts and some successful
applications of a process involving the C–O bond cleavage
with direct use of allylic alcohols catalyzed by palladium
complexes in the presence of Ti(OPri)4 in benzene.22
However, reactions in water have recently attracted much
attention, not only because unique reactivity is often
observed in water but also because water is a safe and
economical solvent.23 Thus, development of atom-econo-
mical reactions in water is one of the most important goals
of synthetic chemistry. Due to our continuing interest in the
palladium-catalyzed allylation of anilines, we disclose a
new catalytic system for palladium-catalyzed allylation
of anilines with allylic alcohols in water as a suspension
A principal goal of organometallic chemistry is the catalytic
synthesis of organic compounds by using the chemistry of
organic ligands covalently bound to transition metals. Most
organometallic chemistry has focused on complexes with
covalent metal–carbon or metal–hydrogen bonds. Tran-
sition metals, in particular palladium and rhodium, have
been workhorse elements in many commercialized catalytic
processes that include hydrogenations, hydroformylations,
acetic acid production, and other C–C and C–H bond
forming processes.1 Although carbon–oxygen, carbon–
nitrogen, or carbon–sulfur bonds are found in the majority
of important organic molecules, catalytic organometallic
reaction chemistry that leads to the formation of carbon-
heteroatom bonds is less common than that forming carbon–
carbon and carbon–hydrogen bonds. Transition metal h3-
allyl complexes, as well as transition metal s-alkyl
complexes, play important roles as active species and key
intermediates in many reactions catalyzed by transition
metal complexes.2 The palladium-catalyzed allylation is a
powerful tool for C–C, C–N, and C–O bond formation,
which has been widely applied to organic chemistry.3 The
processes have been shown to proceed by attack of
nucleophiles on intermediate h3-allylpalladium(II)
complexes generated by oxidative addition of allylic
compounds including halides,4 esters,5 carbonates,6
carbamates,7 phosphates,8 and related derivatives9 to a
Pd(0) complex. Because these substrates are synthesized
from the corresponding allylic alcohols, palladium-catalyzed
Keywords: Palladium-catalyzed; Allylation; Water; Anilines; Allylic
alcohols.
Corresponding author. Tel.: C886 7 3121101; fax: C886 7 3210683;
e-mail: scyang@kmu.edu.tw
*
0040–4020/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.02.035

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S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
medium.24 This is, to our knowledge, the first example of
palladium/carboxylic acid-catalyzed allylation of anilines
by the direct use of allylic alcohols in water.
lauric acid (entry 9) were also effective for the allylation.
(S)-(K)-2-bromopropionic acid (entry 10) and PhCO2H
(entry 11) gave moderate yields of products. CH3CO2H
(entry 12), 4-octylbenzoic acid (entry 13), and Ph2CHCO2H
(entry 14) retarded the allylation. Strong acids such as
C6F5OH (entry 15) and dodecylbenzenesulfonic acid
(DBSA) (entry 16) also enhanced the substitution reaction.
2. Results and discussion
To evaluate the scope and limitations of the N-allylation of
anilines with allylic alcohols, we treated a mixture of aniline
(1a, 1 mmol) and cinnamyl alcohol (2a, 0.8 mmol) in the
presence of Pd(acac)2 (0.02 mmol), PPh3 (0.08 mmol), and
1-adamantanecarboxylic acid (1-AdCO2H) (0.1 mmol) in
water at 50 8C for 30 min. The mixtures of N-cinnamyl-
aniline (3a) and N,N-dicinnamylaniline (4a) were formed in
35 and 7%, respectively (entry 1 in Table 1). The reaction,
under reflux, increased the yields of products 3a and 4a to
54 and 42%, respectively (entry 2). It was confirmed that
the yield was decreased in the absence of PPh3 (entry 3).
The reaction did not occur in the absence of the palladium
species as a catalyst or without water solvent (entries 4
and 5). The effect of water may activate allyl alcohol via
hydration of the hydroxyl group for the smooth generation
of the p-allylpalladium intermediate.25 The absence of a
carboxylic acid gave only a 10% yield of 3a (entry 6). The
effect of addition of 1-AdCO2H to promote the palladium-
catalyzed allyl–OH bond cleavage remarkably enhanced
both the reaction rate and yield. Other carboxylic acids such
as PhSCH2CO2H (entry 7), PhOCH2CO2H (entry 8), and
A comparative study of different palladium catalysts and
phosphine ligands in water was reported (Table 2). Among
the palladium catalysts including Pd(acac)2 (entry 1),
PdCl2(1,10-phen) (entry 2), Pd(OAc)2 (entry 3),
Pd(OCOCF3)2 (entry 4), PdCl2(MeCN)2 (entry 5), PdCl2-
(PhCN)2 (entry 6), PdCl2 (entry 7), Pd(propionate)2 (entry
8), Pd(hfacac)2 (entry 9), Pd2(dba)3 (entries 10 and 11), and
Pd(PPh3)4 (entries 12 and 13) were used. Pd(acac)2,
PdCl2(1,10-phen), PdCl2, Pd(PPh3)4, and Pd(propionate)2
were found to be superior. However, using Pd2(dba)3 or
Pd(PPh3)4 with extra PPh3 as catalyst increased the yield of
products (entries 11 and 13). The catalytic reactivity of the
phosphine ligands is likely due to improved catalyst
stability. In the presence of various monodentate ligands
including PPh3, Bu3P, (PhO)3P, (2-MeC6H4)3P, (2-furyl)3P,
(2-pyridyl)Ph2P, (3-MeC6H4)3P, (4-MeC6H4)3P, (4-
MeOC6H4)3P, (4-FC6H4)3P, (4-ClC6H4)3P, and [2,4,6-
(MeO)3C6H2]3P (entries 1 and 14–24) showed that PPh3
(entry 1), (PhO)3P (entry 15), (3-MeC6H4)3P (entry 19), and
(4-MeOC6H4)3P (entry 21) were the most effective ligands.
The bidentate ligand dppp, dppb, and dpph gave moderate
yields of products (entries 25–29). (G)-BINAP afforded
high yields of products (entry 30).
Table 1. Allylation of aniline (1a) with cinnamyl alcohol (2a): temperature
and acid effectsa
We also studied the influence of the substituent on aniline
on the reactivity of the amination of cinnamyl alcohol (2a)
using Pd(acac)2, PPh3, and 1-AdCO2H. Allylation of
4-substituted anilines containing both electron-withdrawing
and electron-donating groups 1b–g worked well with
cinnamyl alcohol (2a) under reflux giving the corresponding
N-allylanilines and N,N-diallylanilines in overall yields
ranging from 65 to 96% (entries 1–6 in Table 3). These
differences in reactivity could be related to the nucleophi-
licity of the corresponding aniline. 4-Nitroaniline (1g) gave
65% yield; the lower yield observed may arise from the
nature of the nitro group. The more acidic nitroaniline is
probably less reactive in attack on the p-allyl complex than
the methoxyaniline, for example. The sterically more
demanding 2-substituted anilines 1h–n gave lower yields
(entries 7–13). The reaction of 2-nitroaniline (1i), because
of its strong electron-withdrawing and sterically group, gave
only 27% yields. Conversely, anilines having groups on the
3-position, such as 3-OCH2Ph (1o), 3-NO2 (1p), and 3,5-di-
OMe (1q), also gave the products in the high yields of 81, 92
and 77%, respectively (entries 14–16). Secondary aromatic
amine, such as diphenylamine (1r) and phenothiazine (1s),
also reacted to give the N-allylamine in excellent yields
(entries 17 and 18).
Entry
Additive
Yield (%)
(3aC4a)b
Yield (%)
of 3ab
Yield (%)
of 4ab
1c
2
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
1-AdCO2H
—
PhSCH2CO2H
PhOCH2CO2H
CH3(CH2)10CO2H
CH3CH(Br)CO2H
PhCO2H
42
96
6
0
0
10
91
86
84
59
56
14
11
11
80
78
35
54
6
7
42
3d
4e
5f
6g
7
10
55
49
50
21
41
9
11
11
62
55
36
37
34
38
15
5
8
9
10
11
12
13
14
15
16
CH3CO2H
4-OctC6H4CO2H
Ph2CHCO2H
C6F5OH
18
23
DBSA
a Reaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd(acac)2 (0.02 mmol),
PPh3 (0.08 mmol), and additive (0.1 mmol) in water (5 mL) were refluxed
for 30 min.
Results for amination of both aromatic and aliphatic allylic
alcohols 2b–j with aniline (1a) using Pd(acac)2, PPh3, and
1-AdCO2H are summarized in Table 4. In addition to the
parent cinnamyl alcohol (2a), trans-1,3-diphenyl-2-propen-1-
ol (2b) reacted to give the allylating product 5 in excellent
yields (entry 1). In contrast to the previous systems for
b Isolated yield was based on 2a.
c Stirred at 50 8C for 30 min.
d Without PPh3.
e Without Pd(acac)2.
Without water.
g Without acid.
f

S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
3951
Table 2. Allylation of aniline (1a) with cinnamyl alcohol (2a): palladium and phosphine ligand effectsa
Entry
Palladium
Ligand
Yield (%) (3aC4a)b
Yield (%) of 3ab
Yield (%) of 4ab
1
2
3
4
5
6
7
8
Pd(acac)2
PdCl2(1,10-phen)
Pd(OAc)2
Pd(OCOCF3)2
PdCl2(MeCN)2
PdCl2(PhCN)2
PdCl2
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
—
PPh3
—
PPh3
Bu3P
96
99
70
86
78
66
95
91
37
22
69
75
98
67
89
39
55
39
89
63
86
54
37
28
2
54
43
34
63
41
41
44
56
34
22
42
49
59
34
51
26
29
21
51
38
37
31
25
28
2
42
56
36
23
37
25
51
35
3
Pd(propionate)2
c
Pd(hfacac)2
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Pd2(dba)3
Pd2(dba)3
Pd(PPh3)4
Pd(PPh3)4
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
Pd(acac)2
27
26
39
33
38
13
26
18
38
25
49
23
12
(PhO)3P
(2-MeC6H4)3P
(2-Furyl)3P
(2-Pyridyl)Ph2P
(3-MeC6H4)3P
(4-MeC6H4)3P
(4-MeOC6H4)3P
(4-FC6H4)3P
(4-ClC6H4)3P
[2,4,6-(MeO)3C6H2]3P
Dppmd
Dppee
1
1
Dpppf
41
59
45
92
34
43
35
46
7
16
12
46
Dppbg
Dpphh
(G)-BINAPi
a Reaction conditions: 1a (1 mmol), 2a (0.8 mmol), Pd catalyst (0.02 mmol), ligand (0.08 mmol), and 1-AdCO2H (0.1 mmol) in water (5 mL) were refluxed for
30 min.
b Isolated yield was based on 2a.
c Palladium hexafluoroacetylacetonate.
d Bis(diphenylphosphino)methane.
e 1,2-Bis(diphenylphosphino)ethane.
f
1,3-Bis(diphenylphosphino)propane.
g 1,4-Bis(diphenylphosphino)butane.
h 1,6-Bis(diphenylphosphino)hexane.
i
(G)-2,20-Bis(diphenylphosphino)-1,10-binaphthyl.
allylic substitution, reactions of aliphatic allylic alcohols
occurred only moderate yields (entries 2–9). Allylation of
aniline with allyl alcohol (2c) and methallyl alcohol (2d), the
corresponding monoallylated and diallylated products were
formed in overall 45 and 62% yields, respectively (entries 2
and3). Using2-chloro-2-propen-1-ol(2e) as allylating reagent
gaveonlymonoallylatedproductN-(2-chloroallyl)aniline(10)
in 40% yield (entry 4). The sterically more demanding
secondary alcohol 2f gave lower yields (entry 5). Treatment of
aniline (1a) with crotyl alcohol (2g) gave mixtures of stereo-
and regioisomeric anilines 12and 13in the yield of 41and 9%,
respectively (entry 6). 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 80:20 E/Z ratio of 12 was
determined by GC. The product E alkene arising from the
more thermodynamically stable syn p-allyl complex. Since
both regioisomeric alcohols 2g and 2h gave identical mixtures
of the anilines 12 and 13 in similar ratios, the reaction is
considered to proceed via p-allylpalladium intermediates
(entry 7). The loss of the stereochemistry of the starting
alcohol 2g is due to a rapid s%h3 %s interconversion of the
p-allyl intermediate compared to the rate of amination of this
intermediate. With the unsymmetrical allylic alcohols 2, the
major products were obtained from approach of 1 at the less
sterically hindered primary site. Similarly, both regioisomeric
alcohols 2i and 2j reacted with aniline to give identical
mixtures of 14 and regioisomeric aniline 15, as expected from
attack of the aniline on the two allylic termini of the
p-allylpalladium species, in similar ratios (entries 8 and 9).
A possible mechanism for the formation of N-allylanilines
from 1 and 2 is illustrated in Scheme 1, in which the
substituent on allylic alcohol is omitted. Oxidative addition
of alcohol 2 or protonated alcohol, formed by the acid, to
Pd(0) species affords the p-allylpalladium intermediate
(16). The formation of the p-allylpalladium may be
accelerated by the acid, possibly by protonation to increase
the leaving group ability of the OH group of the allyl
alcohol.26 Formation of a p-allylpalladium with the
carboxylic acid could be the key for the rate enhancement
by the acid.27 Intermolecular nucleophilic substitution of the
amino group of 1 takes place at the p-allyl system to give
intermediate 17, followed by reductive elimination gives
N-allylaniline. In the presence of anilines, which may be
relatively reactive toward the palladium center, 16 should be
predominantly transformed to 17 to afford aryl amine.
3. Conclusions
In summary, we have developed a catalytic system that
enables reactions of aromatic amines with allylic alcohols as

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S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
Table 3. Allylic amination of cinnamyl alcohol (2a) with anilines (1b–s)a
Entry
1
R1
R2
Yield (%) (3C4)b
Yield of 3b
Yield of 4b
1
2
3
4
5
6
7
8
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
1p
1q
1r
1s
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Ph
4-Me
4-Cl
4-OMe
4-CO2Et
4-CN
4-NO2
2-Br
2-CN
2-NO2
2,4-Di-Me
2-Cl, 4-Me
2-Me, 4-OMe
2-OMe, 4-NO2
3-OCH2Ph
3-NO2
81
78
96
91
87
65
30
78
27
60
73
65
73
81
92
77
92
95
3b 41%
3c 63%
3d 69%
3e 81%
3f 70%
3g 51%
3h 30%
3i 78%
3j 27%
3k 55%
3l 73%
3m 59%
3n 73%
3o 65%
3p 76%
3q 56%
3r 92%
3s 95%
4b 40%
4c 15%
4d 27%
4e 10%
4f 17%
4g 14%
9
10
11
12
13
14
15
16
17
18
4k 5%
4m 6%
4o 16%
4p 16%
4q 21%
3,5-Di-OMe
H
a Reaction conditions: 1 (1 mmol), 2a (0.8 mmol), Pd(acac)2 (0.02 mmol), PPh3 (0.08 mmol), and 1-AdCO2H (0.1 mmol) in water (5 mL) were refluxed for
30 min.
b Isolated yield was based on 2a.
Table 4. Reaction of aniline (1a) with allylic alcohols (2b–j)a
Entry
2
Yieldsb
1
2b
5 99%
2c
2
3
4
7 14%
6 31%
8 46%
2d
9 16%
2e
2f
10 40%
5
11 26%

S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
3953
Table 4 (continued)
Entry
2
Yieldsb
2g
6
7
12 41% (E/ZZ80/20)c
12 40% (E/ZZ78/22)c
13 9%
13 11%
2h
2i
8
9
15 8%
15 7%
14 35%
14 38%
2j
a Reaction conditions: 1a (1 mmol), 2 (0.8 mmol), Pd(acac)2 (0.02 mmol), PPh3 (0.08 mmol), 1-AdCO2H (0.1 mmol) and water (5 mL) were refluxed for
30 min.
b Isolated yield was based on 2.
c Determined by GC.
spectrophotometer. Proton and carbon-13 NMR were
measured with a Unity-400 or Mercury Plus-400 spec-
trometer. Carbon multiplicities were obtained from DEPT
experiments. Chemical shifts (d) and coupling constants (Hz)
weremeasuredwithrespect toTMS orchloroform-d1. MSand
high-resolution mass spectra (HRMS) were taken on a
Thermo-Finnigan trace GC or Finnigan MAT-95XL instru-
ment, with a direct inlet system. Elemental analyses were
carried out on a Heraeus CHN-O-Rapid elemental analyzer.
All the following chemicals were commercially available and
used without further purification. Pd(acac)2 (acacZacetyl-
acetonate), Pd2(dba)3 (dbaZdibenzylideneacetone),
(2-MeC6H4)3P, (2-furyl)3P, (4-MeOC6H4)3P, (4-FC6H4)3P,
dppm, 1-adamantanecarboxylic acid, C6F5OH, 3,5-
dimethoxyaniline, and diphenylamine were purchased from
Lancaster. PdCl2(1,10-phen) (phenZphenanthroline),
Pd(OCOCF3)2,
PdCl2(MeCN)2,
PdCl2(PhCN)2,
Pd(propionate)2, Pd(hfacac)2, (2-pyridyl)Ph2P, (3-
MeC6H4)3P, (4-MeC6H4)3P, [2,4,6-(MeO)3C6H2]3P, dppp,
dppb, dpph, phenoxyacetic acid, diphenylacetic acid,
2-chloro-4-methylaniline, 4-methoxy-2-methylaniline,
3-benzyloxyaniline, and 2-chloro-2-propen-1-ol were
purchased from Aldrich. Pd(OAc)2, PPh3, (PhO)3P, and
allyl alcohol were purchased from Riedel-de Haen. PdCl2,
(4-ClC6H4)3P, (G)BINAP, lauric acid, 4-octylbenzoic acid,
4-chloroaniline, 2-cyanoaniline, 2-nitroaniline, and pheno-
thiazine were purchased from Acros Organics. Pd(PPh3)4,
Bu3P, dppe, (phenylthio)acetic acid, (S)-(K)-2-bromo-
propionic acid, sodium dodecylbenzenesulfonate, aniline,
p-tolulidine, p-anisidine, 4-aminobenzoic acid ethyl ester,
4-cyanoaniline, 4-nitroaniline, 2-bromoaniline, 2,4-dimethyl-
aniline, 2-methoxy-4-nitroaniline, 3-nitroaniline, cinnamyl
alcohol, 2-buten-1-ol, 3-buten-2-ol, 2-cyclohexen-1-ol,
methallyl alcohol, 2-methyl-3-buten-2-ol, 3-methyl-2-buten-
1-ol, and 2-methyl-3-buten-2-ol were purchased from TCI.
trans-1,3-Diphenyl-2-propen-1-ol was purchased from Fluka.
Benzoic acid and acetic acid were purchased from Showa.
Scheme 1.
allylating agents in water. This is a simple and efficient route
for C–N bond formation. The effect of addition of a
carboxylic acid to promote the palladium-catalyzed allyl–
OH bond cleavage remarkably enhanced both the reaction
rate and yield. The amination of aromatic and aliphatic
allylic alcohol worked well with anilines, giving generally
good to high yields of the corresponding allylic anilines.
Anilines with steric constraints gave lower chemical yields.
4. Experimental
4.1. General considerations. General method
All melting points were uncorrected. IR absorption spectra
were recorded on a Perkin-Elmer System 2000 FT-IR

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S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
4.2. General procedure for the palladium-catalyzed
allylation of anilines. Reaction with aniline (1a)
(d, JZ16.0 Hz, 2H, vinyl H), 6.74 (d, JZ8.8 Hz, 2H, ArH),
7.03 (d, JZ8.0 Hz, 2H, ArH), 7.17–7.21 (m, 2H, ArH), 7.27
(dd, JZ7.2, 7.6 Hz, 4H, ArH), 7.33 (dd, JZ1.6, 8.0 Hz, 4H,
ArH). 13C NMR (CDCl3) d: 20.2 (CH3), 52.4 (CH2), 112.9
(CH), 125.8 (C), 126.1 (CH), 126.3 (CH), 127.3 (CH), 128.5
(CH), 129.7 (CH), 131.1 (CH), 136.9 (C), 146.7 (C). EI-MS
m/z: 339 (MC), 327, 320, 299, 281, 267, 250, 234, 207, 171,
158, 128, 115, 91, 73. HR-MS calcd for C25H25N 339.1987,
found 339.1988. Anal. Calcd for C25H25N: C, 88.45; H,
7.42; N, 4.13. Found: C, 88.44; H, 7.64; N, 3.98.
Cinnamyl alcohol (2a) (107 mg, 0.8 mmol) and 1-adaman-
tanecarboxylic acid (18 mg, 0.1 mmol) were suspended in
water (5 mL) at rt, and then Pd(acac)2 (6 mg, 0.02 mmol),
PPh3 (21 mg, 0.08 mmol) and aniline (93 mg, 1 mmol) were
added. The whole was heated under reflux conditions for
30 min. After the mixture was cooled to rt, water and brine
were added. The organic materials were extracted with
dichloromethane, dried over magnesium sulfate, and
concentrated under vacuum. Column chromatography
(chloroform/n-hexane 1:2) of the residue afforded 3a and
4a in 54 and 42% yields, respectively.
4.2.5. N-Cinnamyl-4-chloroaniline (3c). White crystals.
Mp 77–79 8C (chloroform/hexane). IR (KBr) n: 3421 cmK1
.
1H NMR (CDCl3) d: 3.71 (br s, 1H, NH), 3.86 (dd, JZ1.6,
6.0 Hz, 2H, CH2), 6.26 (dt, JZ6.0, 16.0 Hz, 1H, vinyl H),
6.55 (d, JZ8.8 Hz, 2H, ArH), 6.58 (d, JZ16.0 Hz, 1H,
vinyl H), 7.11 (d, JZ8.8 Hz, 2H, ArH), 7.19–7.24 (m, 1H,
ArH), 7.29 (dd, JZ7.2, 8.0 Hz, 2H, ArH), 7.34 (dd, JZ1.6,
7.2 Hz, 2H, ArH). 13C NMR (CDCl3) d: 46.2 (CH2), 114.1
(CH), 122.1 (C), 126.2 (CH), 126.3 (CH), 127.6 (CH), 128.5
(CH), 129.0 (CH), 131.7 (CH), 136.6 (C), 146.4 (C). EI-MS
m/z: 245 (MCC2), 243 (MC), 226, 208, 191, 166, 140, 130,
117, 115, 91, 77. HR-MS calcd for C15H14ClN 243.0814,
found 243.0815. Anal. Calcd for C15H14ClN: C, 73.92; H,
5.79; N, 5.75. Found: C, 73.95; H, 5.80; N, 5.75.
Products 3f,22e 4f,22e 3g,22e 4g,22e 3j,22e 3p,22e 4p,22e 3r,22e
3s,22e 6,22a 7,22a 12,22b and 13,22b are known.
4.2.1. N-Cinnamylaniline (3a).28 Light brown oil. IR (KBr)
1
n: 3421 cmK1. H NMR (CDCl3) d: 3.58 (br s, 1H, NH),
3.89 (dd, JZ1.6, 5.6 Hz, 2H, CH2), 6.29 (dt, JZ5.6,
16.0 Hz, 1H, vinyl H), 6.59 (dt, JZ1.6, 16.0 Hz, 1H, vinyl
H), 6.63–6.66 (m, 2H, ArH), 6.72 (ddt, JZ0.8, 1.2, 7.2 Hz,
1H, ArH), 7.17–7.23 (m, 3H, ArH), 7.28 (dd, JZ7.6,
7.6 Hz, 2H, ArH), 7.34 (dd, JZ1.6, 8.0 Hz, 2H, ArH). 13C
NMR (CDCl3) d: 46.1 (CH2), 113.0 (CH), 117.6 (CH),
126.3 (CH), 126.9 (CH), 127.5 (CH), 128.5 (CH), 129.2
(CH), 131.4 (CH), 136.8 (C), 147.9 (C). EI-MS m/z: 209
(MC), 132, 117, 115, 91. HR-MS calcd for C15H15N
209.1204, found 209.1204.
4.2.6. N,N-Dicinnamyl-4-chloroaniline (4c). Light yellow
crystals. Mp 79–81 8C (chloroform/hexane). 1H NMR
(CDCl3) d: 4.11 (dd, JZ1.6, 5.2 Hz, 4H, CH2!2), 6.24
(dt, JZ5.2, 16.0 Hz, 2H, vinyl H), 6.51 (d, JZ16.0 Hz, 2H,
vinyl H), 6.72 (d, JZ8.4 Hz, 2H, ArH), 7.16 (d, JZ9.2 Hz,
2H, ArH), 7.20–7.25 (m, 2H, ArH), 7.30 (dd, JZ7.2,
7.6 Hz, 4H, ArH), 7.35 (dd, JZ1.6, 7.2 Hz, 4H, ArH). 13C
NMR (CDCl3) d: 52.4 (CH2), 113.7 (CH), 121.3 (C), 125.2
(CH), 126.3 (CH), 127.6 (CH), 128.6 (CH), 129.0 (CH),
131.4 (CH), 136.7 (C), 147.3 (C). EI-MS m/z: 361 (MCC2),
359 (MC), 327, 299, 281, 268, 254, 240, 225, 217, 207, 204,
192, 190, 178, 166, 154, 142, 140, 127, 125, 115, 111, 91,
77. HR-MS calcd for C24H22ClN 359.1440, found
359.1441. Anal. Calcd for C24H22ClN: C, 80.10; H, 6.16;
N, 3.89. Found: C, 79.96; H, 6.19; N, 3.77.
4.2.2. N,N-Dicinnamylaniline (4a).29 Light yellow crys-
tals. Mp 81–83 8C (chloroform/hexane). H NMR (CDCl3)
1
d: 4.13 (d, JZ5.2 Hz, 4H, CH2!2), 6.28 (dt, JZ5.2,
16.0 Hz, 2H, vinyl H), 6.54 (d, JZ16.0 Hz, 2H, vinyl H),
6.72 (dd, JZ6.8, 7.2 Hz, 1H, ArH), 6.82 (d, JZ8.0 Hz, 2H,
ArH), 7.19–7.25 (m, 4H, ArH), 7.29 (dd, JZ7.2, 8.0 Hz,
4H, ArH), 7.36 (dd, JZ1.2, 7.2 Hz, 4H, ArH). 13C NMR
(CDCl3) d: 52.2 (CH2), 112.6 (CH), 116.6 (CH), 125.8
(CH), 126.3 (CH), 127.4 (CH), 128.5 (CH), 129.2 (CH),
131.2 (CH), 136.8 (C), 148.8 (C). EI-MS m/z: 325 (MC),
234, 220, 206, 144, 117, 115, 91, 77. HR-MS calcd for
C24H23N 325.1830, found 325.1832. Anal. Calcd for
C24H23N: C, 88.57; H, 7.12; N, 4.30. Found: C, 88.18; H,
7.16; N, 4.19.
4.2.7. N-Cinnamyl-4-methoxyaniline (3d). Light yellow
crystals. Mp 63–64 8C (chloroform/hexane). IR (KBr) n:
3400 cmK1. 1H NMR (CDCl3) d: 3.42 (br s, 1H, NH), 3.72
(s, 3H, OCH3), 3.85 (dd, JZ1.6, 6.0 Hz, 2H, CH2), 6.31 (dt,
JZ6.0, 16.0 Hz, 1H, vinyl H), 6.59 (d, JZ16.0 Hz, 1H,
vinyl H), 6.62 (d, JZ8.8 Hz, 2H, ArH), 6.78 (d, JZ8.8 Hz,
2H, ArH), 7.18–7.22 (m, 1H, ArH), 7.29 (dd, JZ7.2,
8.0 Hz, 2H, ArH), 7.35 (dd, JZ1.2, 7.2 Hz, 2H, ArH). 13C
NMR (CDCl3) d: 47.1 (CH2), 55.6 (CH3), 114.3 (CH), 114.8
(CH), 126.2 (CH), 127.3 (CH), 127.4 (CH), 128.5 (CH),
131.3 (CH), 136.8 (C), 142.1 (C), 152.2 (C). EI-MS m/z: 239
(MC), 222, 208, 197, 162, 147, 122, 117, 115, 91, 77. HR-
MS calcd for C16H17NO 239.1310, found 239.1312. Anal.
Calcd for C16H17NO: C, 80.32; H, 7.16; N, 5.85. Found: C,
80.29; H, 7.17; N, 5.79.
4.2.3. N-Cinnamyl-4-methylaniline (3b). Deep yellow oil.
1
IR (KBr) n: 3406 cmK1. H NMR (CDCl3) d: 2.23 (s, 3H,
CH3), 3.43 (br s, 1H, NH), 3.87 (dd, JZ1.6, 6.0 Hz, 2H,
CH2), 6.30 (dt, JZ6.0, 16.0 Hz, 1H, vinyl H), 6.58 (dt, JZ
1.6, 16.0 Hz, 1H, vinyl H), 6.58 (d, JZ8.4 Hz, 2H, ArH),
6.99 (d, JZ8.0 Hz, 2H, ArH), 7.18–7.22 (m, 1H, ArH), 7.28
(dd, JZ7.2, 7.6 Hz, 2H, ArH), 7.34 (dd, JZ1.6, 8.0 Hz, 2H,
ArH). 13C NMR (CDCl3) d: 20.4 (CH3), 46.5 (CH2), 113.2
(CH), 126.3 (CH), 126.8 (C), 127.2 (CH), 127.4 (CH), 128.5
(CH), 129.7 (CH), 131.3 (CH), 136.8 (C), 145.7 (C). EI-MS
m/z: 223 (MC), 208, 196, 181, 165, 146, 131, 117, 115, 91,
77. HR-MS calcd for C16H17N 223.1361, found 223.1361.
4.2.8. N,N-Dicinnamyl-4-methoxyaniline (4d). Light
brown oil. H NMR (CDCl3) d: 3.75 (s, 3H, OCH3), 4.06
(dd, JZ1.6, 5.6 Hz, 4H, CH2!2), 6.26 (dt, JZ5.6, 16.0 Hz,
2H, vinyl H), 6.53 (d, JZ16.0 Hz, 2H, vinyl H), 6.76–6.84
(m, 4H, ArH), 7.18–7.23 (m, 2H, ArH), 7.29 (dd, JZ7.2,
1
4.2.4. N,N-Dicinnamyl-4-methylaniline (4b). Light yellow
crystals. Mp 66–68 8C (chloroform/hexane). 1H NMR
(CDCl3) d: 2.24 (s, 3H, CH3), 4.07 (dd, JZ1.6, 5.2 Hz,
4H, CH2!2), 6.25 (dt, JZ5.2, 16.0 Hz, 2H, vinyl H), 6.51

S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
3955
8.0 Hz, 4H, ArH), 7.35 (dd, JZ1.2, 7.2 Hz, 4H, ArH). 13C
NMR (CDCl3) d: 53.2 (CH2), 55.7 (CH3), 114.7 (CH), 115.0
(CH), 126.2 (CH), 126.3 (CH), 127.4 (CH), 128.5 (CH),
131.4 (CH), 136.9 (C), 143.4 (C), 151.9 (C). EI-MS m/z: 355
(MC), 327, 315, 281, 264, 250, 238, 221, 207, 174, 160,
149, 134, 121, 117, 115, 91, 77. HR-MS calcd for
C25H25NO 355.1936, found 355.1937.
ArH), 7.21–7.25 (m, 1H, ArH), 7.31 (dd, JZ7.2, 7.6 Hz,
2H, ArH), 7.33–7.40 (m, 4H, ArH). 13C NMR (CDCl3) d:
45.1 (CH2), 95.7 (C), 110.8 (CH), 116.5 (CH), 117.8 (C),
125.1 (CH), 126.2 (CH), 127.6 (CH), 128.4 (CH), 131.9
(CH), 132.6 (CH), 134.1 (CH), 136.2 (C), 149.9 (C). EI-MS
m/z: 234 (MC), 217, 207, 155, 131, 117, 115, 102, 91. HR-
MS calcd for C16H14N2 234.1157, found 234.1159. Anal.
Calcd for C15H14N2: C, 82.02; H, 6.02; N, 11.96. Found: C,
82.18; H, 6.00; N, 11.94.
4.2.9. Ethyl 4-(cinnamylamino)benzoate (3e). White
crystals. Mp 132–133 8C (chloroform/hexane). IR (KBr) n:
1
3429 cmK1. H NMR (CDCl3) d: 1.34 (t, JZ7.2 Hz, 3H,
4.2.13. N-Cinnamyl-2,4-dimethylaniline (3k). Brown oil.
1
CH3), 3.96 (dd, JZ1.6, 5.6 Hz, 2H, CH2), 4.30 (dd, JZ7.2,
7.2 Hz, 2H, CH2), 4.49 (br s, 1H, NH), 6.26 (dt, JZ5.6,
15.6 Hz, 1H, vinyl H), 6.59 (dt, JZ1.2, 16.0 Hz, 1H, vinyl
H), 7.20–7.25 (m, 1H, ArH), 7.30 (dd, JZ7.2, 7.6 Hz, 2H,
ArH), 7.35 (dd, JZ1.6, 7.2 Hz, 2H, ArH), 7.88 (d, JZ
9.2 Hz, 2H, ArH). 13C NMR (CDCl3) d: 14.4 (CH3), 45.5
(CH2), 60.2(CH2), 111.7 (CH), 119.0 (C), 125.6 (CH), 126.3
(CH), 127.7 (CH), 128.5 (CH), 131.4 (CH), 132.0 (CH),
136.5 (C), 151.5 (C), 166.8 (C). EI-MS m/z: 281 (MC), 252,
236, 208, 191, 150, 130, 117, 115, 91. HR-MS calcd for
C18H19NO2 281.1416, found 281.1415. Anal. Calcd for
C18H19NO2: C, 76.84; H, 6.81; N, 4.98. Found: C, 76.77; H,
6.81; N, 4.90.
IR (KBr) n: 3431 cmK1. H NMR (CDCl3) d: 2.12 (s, 3H,
CH3), 2.22 (s, 3H, CH3), 3.40 (br s, 1H, NH), 3.90 (dd, JZ
1.6, 6.0 Hz, 2H, CH2), 6.33 (dt, JZ6.0, 16.0 Hz, 1H, vinyl
H), 6.57 (d, JZ8.0 Hz, 1H, ArH), 6.59 (dt, JZ1.6, 16.0 Hz,
1H, vinyl H), 6.89 (s, 1H, ArH), 6.92 (dd, JZ1.6, 8.0 Hz,
1H, ArH), 7.17–7.23 (m, 1H, ArH), 7.27 (dd, JZ7.2,
7.6 Hz, 2H, ArH), 7.34 (dd, JZ1.6, 7.2 Hz, 2H, ArH). 13C
NMR (CDCl3) d: 17.4 (CH3), 20.3 (CH3), 46.4 (CH2), 110.3
(CH), 122.2 (C), 126.2 (CH), 127.1 (C), 127.2 (CH), 127.3
(CH), 127.4 (CH), 128.5 (CH), 130.9 (CH), 131.2 (C), 131.4
(CH), 136.8 (C). EI-MS m/z: 237 (MC), 144, 132, 117, 115,
91. HR-MS calcd for C17H19N 237.1518, found 237.1517.
4.2.14. N,N-Dicinnamyl-2,4-dimethylaniline (4k). Light
brown oil. H NMR (CDCl3) d: 2.27 (s, 3H, CH3), 2.36 (s,
1
4.2.10. Ethyl 4-(dicinnamylamino)benzoate (4e). White
crystals. Mp 120–122 8C (chloroform/hexane). 1H NMR
(CDCl3) d: 1.35 (t, JZ7.2 Hz, 3H, CH3), 4.20 (dd, JZ1.2,
5.2 Hz, 2H, CH2!2), 4.32 (dd, JZ7.2 Hz, 2H, CH2), 6.25
(dt, JZ5.2, 16.0 Hz, 2H, vinyl H), 6.51 (d, JZ16.0 Hz, 2H,
vinyl H), 6.79 (d, JZ9.2 Hz, 2H, ArH), 7.21–7.25 (m, 2H,
ArH), 7.30 (dd, JZ7.2, 7.6 Hz, 4H, ArH), 7.35 (dd, JZ1.6,
7.2 Hz, 4H, ArH), 7.92 (d, JZ8.8 Hz, 2H, ArH). 13C NMR
(CDCl3) d: 14.4 (CH3), 52.2 (CH2), 60.1 (CH2), 108.1 (C),
111.3 (CH), 124.2 (CH), 126.3 (CH), 127.6 (CH), 128.5
(CH), 131.3 (CH), 131.7 (CH), 136.4 (C), 151.7 (C), 166.7
(C). EI-MS m/z: 397 (MC), 368, 352, 341, 327, 319, 306,
292, 281, 267, 253, 230, 207, 192, 178, 163, 150, 135, 117,
91, 77. HR-MS calcd for C27H27NO2 397.2041, found
397.2043. Anal. Calcd for C27H27NO2: C, 81.58; H, 6.85; N,
3.52. Found: C, 81.75; H, 6.90; N, 3.45.
3H, CH3), 3.74 (d, JZ6.4 Hz, 4H, CH2!2), 6.21 (dt, JZ
6.4, 16.0 Hz, 2H, vinyl H), 6.51 (d, JZ16.0 Hz, 2H, vinyl
H), 6.93–7.01 (m, 3H, ArH), 7.18–7.25 (m, 2H, ArH), 7.28
(dd, JZ7.2, 7.6 Hz, 4H, ArH), 7.34 (d, JZ7.2 Hz, 4H,
ArH). 13C NMR (CDCl3) d: 18.3 (CH3), 20.7 (CH3), 55.3
(CH2), 121.9 (CH), 126.3 (CH), 126.6 (CH), 127.3 (CH),
128.1 (CH), 128.5 (CH), 131.8 (CH), 132.1 (CH), 132.6 (C),
133.7 (C), 137.2 (C), 147.5 (C). EI-MS m/z: 353 (MC), 262,
248, 237, 220, 172, 158, 147, 132, 117, 115, 103, 91, 77.
HR-MS calcd for C26H27N 353.2144, found 353.2144.
4.2.15. N-Cinnamyl-2-chloro-4-methylaniline (3l).
1
Yellow oil. IR (KBr) n: 3418 cmK1. H NMR (CDCl3) d:
2.20 (s, 3H, CH3), 3.93 (dd, JZ1.6, 5.6 Hz, 2H, CH2), 4.36
(br s, 1H, NH), 6.29 (dt, JZ5.6, 16.0 Hz, 1H, vinyl H), 6.59
(d, JZ15.6 Hz, 1H, vinyl H), 6.60 (d, JZ8.4 Hz, 1H, ArH),
6.92 (dd, JZ2.0, 8.4 Hz, 1H, ArH), 7.09 (d, JZ2.0 Hz, 1H,
ArH), 7.18–7.23 (m, 1H, ArH), 7.30 (dd, JZ7.2, 7.6 Hz,
2H, ArH), 7.35 (dd, JZ1.2, 7.2 Hz, 2H, ArH). 13C NMR
(CDCl3) d: 20.1 (CH3), 46.0 (CH2), 111.6 (CH), 119.0 (C),
126.3 (CH), 126.5 (CH), 127.5 (CH), 128.3 (CH), 128.5
(CH), 129.5 (CH), 131.5 (CH), 136.7 (C), 141.5 (C). EI-MS
m/z: 259 (MCC2), 257 (MC), 222, 205, 178, 154, 144, 117,
115, 91, 77. HR-MS calcd for C16H16ClN 257.0971, found
257.0970.
4.2.11. N-Cinnamyl-2-bromoaniline (3h). Light brown oil.
IR (KBr) n: 3422 cmK1. 1H NMR (CDCl3) d: 3.99 (dd, JZ
1.6, 5.6 Hz, 2H, CH2), 4.68 (br s, 1H, NH), 6.31 (dt, JZ5.6,
16.0 Hz, 1H, vinyl H), 6.59 (ddd, JZ1.2, 7.2, 7.6 Hz, 1H,
ArH), 6.62 (dd, JZ1.6, 16.0 Hz, 1H, vinyl H), 6.70 (dd, JZ
1.6, 8.4 Hz, 1H, ArH), 7.17 (ddd, JZ1.6, 7.2, 7.6 Hz, 1H,
ArH), 7.20–7.25 (m, 1H, ArH), 7.28–7.33 (m, 2H, ArH),
7.35–7.39 (m, 2H, ArH), 7.44 (dd, JZ1.6, 8.0 Hz, 1H,
ArH). 13C NMR (CDCl3) d: 46.0 (CH2), 109.8 (C), 117.8
(CH), 118.1 (CH), 126.1 (CH), 126.4 (CH), 127.6 (CH),
128.5 (CH), 128.6 (CH), 131.8 (CH), 132.4 (CH), 136.6 (C),
144.6 (C). EI-MS m/z: 290 (MCC2), 288 (MC), 208, 191,
130, 117, 115, 91. HR-MS calcd for C15H14BrN 287.0310,
found 287.0309.
4.2.16. N-Cinnamyl-4-methoxy-2-methylaniline (3m).
Deep brown oil. IR (KBr) n: 3422 cmK1 1H NMR
.
(CDCl3) d: 2.14 (s, 3H, CH3), 3.20 (br s, 1H, NH), 3.71
(s, 3H, OCH3), 3.89 (dd, JZ1.2, 5.6 Hz, 2H, CH2), 6.34 (dt,
JZ6.0, 16.0 Hz, 1H, vinyl H), 6.59 (d, JZ16.0 Hz, 1H,
vinyl H), 6.60 (d, JZ8.4 Hz, 1H, ArH), 6.67–6.71 (m, 2H,
ArH), 7.18–7.22 (m, 1H, ArH), 7.28 (dd, JZ7.2, 7.6 Hz,
2H, ArH), 7.35 (dd, JZ1.6, 7.2 Hz, 2H, ArH). 13C NMR
(CDCl3) d: 17.7 (CH3), 46.9 (CH2), 55.6 (CH3), 111.2 (CH),
111.4 (CH), 116.9 (CH), 123.9 (C), 126.2 (CH), 127.3 (CH),
127.4 (CH), 128.5 (CH), 131.4 (CH), 136.8 (C), 140.1 (C),
4.2.12. N-Cinnamyl-2-cyanoaniline (3i). Colorless crys-
tals. Mp 70–72 8C (chloroform/hexane). IR (KBr) n: 3431,
1
2212 cmK1. H NMR (CDCl3) d: 4.00 (dd, JZ1.6, 5.6 Hz,
2H, CH2), 4.85 (br s, 1H, NH), 6.24 (dt, JZ5.6, 16.0 Hz,
1H, vinyl H), 6.60 (dt, JZ1.6, 16.0 Hz, 1H, vinyl H), 6.67
(ddd, JZ0.8, 7.2, 7.6 Hz, 1H, ArH), 6.69 (d, JZ8.4 Hz, 1H,

3956
S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
151.7 (C). EI-MS m/z: 253 (MC), 136, 117, 115, 93, 91. HR-
MS calcd for C17H19NO 253.1467, found 253.1468.
281, 250, 207, 179, 166, 150, 131, 117, 91. HR-MS calcd for
C31H29NO 431.2249, found 431.2250. Anal. Calcd for
C31H29NO: C, 86.27; H, 6.77; N, 3.25. Found: C, 86.16; H,
6.83; N, 3.20.
4.2.17. N,N-Dicinnamyl-4-methoxy-2-methylaniline
(4m). Yellow oil. H NMR (CDCl3) d: 2.37 (s, 3H, CH3),
1
3.70 (d, JZ6.4 Hz, 4H, CH2!2), 3.74 (s, 3H, OCH3), 6.20
(dt, JZ6.4, 16.0 Hz, 2H, vinyl H), 6.49 (d, JZ16.0 Hz, 2H,
vinyl H), 6.68 (dd, JZ2.8, 8.8 Hz, 1H, ArH), 6.75 (d, JZ
2.8 Hz, 1H, ArH), 7.02 (d, JZ8.8 Hz, 1H, ArH), 7.19–7.23
(m, 2H, ArH), 7.29 (dd, JZ7.2, 7.6 Hz, 4H, ArH), 7.32 (dd,
JZ1.6, 7.6 Hz, 4H, ArH). 13C NMR (CDCl3) d: 18.4 (CH3),
55.2 (CH3), 55.9 (CH2), 111.0 (CH), 116.2 (CH), 123.3 (CH),
126.2 (CH), 127.2 (CH), 127.3 (CH), 128.4 (CH), 132.1 (CH),
135.8 (C), 137.2 (C), 143.2 (C), 155.6 (C). EI-MS m/z: 369
(MC), 278, 264, 252, 207, 188, 148, 135, 133, 117, 115, 91.
HR-MS calcd for C26H27NO 369.2093, found 369.2089.
4.2.21. N-Cinnamyl-3,5-dimethoxyaniline (3q). Light
1
green oil. IR (KBr) n: 3408 cmK1. H NMR (CDCl3) d:
3.70 (s, 6H, CH3!2), 3.82 (br s, 1H, NH), 3.83 (dd, JZ1.6,
5.6 Hz, 2H, CH2), 5.83 (d, JZ2.4 Hz, 2H, ArH), 5.89 (dd,
JZ2.0, 2.4 Hz, 1H, ArH), 6.25 (dt, JZ5.6, 16.0 Hz, 1H,
vinyl H), 6.55 (d, JZ16.0 Hz, 1H, vinyl H), 7.16–7.21 (m,
1H, ArH), 7.27 (dd, JZ7.6, 7.6 Hz, 2H, ArH), 7.33 (dd, JZ
1.6, 7.2 Hz, 2H, ArH). 13C NMR (CDCl3) d: 46.0 (CH2),
54.9 (CH3), 54.9 (CH3), 89.7 (CH), 91.7 (CH), 126.2 (CH),
126.7 (CH), 127.4 (CH), 128.4 (CH), 131.3 (CH), 136.7 (C),
149.9 (C), 161.6 (C). EI-MS m/z: 269 (MC), 252, 238, 223,
190, 178, 166, 147, 117, 115, 91. HR-MS calcd for
C17H19NO2 269.1416, found 269.1416.
4.2.18. N-Cinnamyl-2-methoxy-4-nitroaniline (3n). Light
yellow crystals. Mp 129–131 8C (chloroform/hexane). IR
1
(KBr) n: 3429 cmK1. H NMR (CDCl3) d: 3.91 (s, 3H,
4.2.22. N,N-Dicinnamyl-3,5-dimethoxyaniline (4q).
Brown oil. H NMR (CDCl3) d: 3.75 (s, 6H, OCH3!2),
1
OCH3), 4.04 (dd, JZ1.6, 5.6 Hz, 2H, CH2), 5.28 (br s, 1H,
NH), 6.26 (dt, JZ5.6, 15.6 Hz, 1H, vinyl H), 6.52 (d, JZ
8.8 Hz, 1H, ArH), 6.60 (d, JZ15.6 Hz, 1H, vinyl H), 7.21–
7.26 (m, 1H, ArH), 7.31 (dd, JZ7.2, 7.6 Hz, 2H, ArH), 7.36
(dd, JZ1.6, 7.2 Hz, 2H, ArH), 7.61 (d, JZ2.4 Hz, 1H,
ArH), 7.88 (dd, JZ2.4, 8.8 Hz, 1H, ArH). 13C NMR
(CDCl3) d: 44.9 (CH2), 55.8 (CH3), 104.6 (CH), 106.9 (CH),
119.7 (CH), 124.7 (CH), 126.3 (CH), 127.8 (CH), 128.5
(CH), 132.4 (CH), 136.2 (C), 137.2 (C), 143.9 (C), 145.1
(C). EI-MS m/z: 284 (MC), 253, 237, 207, 193, 165, 147,
117, 115, 91. HR-MS calcd for C16H16N2O3 284.1161,
found 284.1162. Anal. Calcd for C16H16N2O3: C, 67.59; H,
5.67; N, 9.85. Found: C, 67.56; H, 5.64; N, 9.72.
4.10 (dd, JZ1.2, 5.2 Hz, 4H, CH2!2), 5.92 (dd, JZ2.0,
2.0 Hz, 1H, ArH), 6.01 (d, JZ2.0 Hz, 2H, ArH), 6.26 (dt,
JZ5.2, 16.0 Hz, 2H, vinyl H), 6.53 (d, JZ16.0 Hz, 2H,
vinyl H), 7.19–7.23 (m, 2H, ArH), 7.29 (dd, JZ7.2, 7.6 Hz,
4H, ArH), 7.35 (dd, JZ1.6, 7.2 Hz, 4H, ArH). 13C NMR
(CDCl3) d: 52.3 (CH2), 55.1 (CH3), 88.6 (CH), 91.9 (CH),
125.7 (CH), 126.3 (CH), 127.4 (CH), 128.5 (CH), 131.2
(CH), 136.8 (C), 150.7 (C), 161.7 (C). EI-MS m/z: 385
(MC), 356, 318, 307, 294, 268, 253, 238, 222, 210, 190,
177, 166, 153, 117, 115, 91. HR-MS calcd for C26H27NO2
385.2041, found 385.2038.
4.2.23. (1,3-Diphenylallyl)phenylamine (5). Brown oil. IR
1
(KBr) n: 3414 cmK1. H NMR (CDCl3) d: 4.08 (br s, 1H,
4.2.19. N-Cinnamyl-3-benzyloxyaniline (3o). Brown oil.
IR (KBr) n: 3411 cmK1. 1H NMR (CDCl3) d: 3.75 (br s, 1H,
NH), 3.82 (dd, JZ1.2, 6.0 Hz, 2H, CH2), 4.97 (s, 2H, CH2),
6.24 (dt, JZ6.0, 15.6 Hz, 1H, vinyl H), 6.24–6.28 (m, 2H,
ArH), 6.34 (ddd, JZ0.8, 2.4, 8.0 Hz, 1H, ArH), 6.54 (d, JZ
16.0 Hz, 1H, vinyl H), 7.06 (t, JZ8.0 Hz, 1H, ArH), 7.17–
7.21 (m, 1H, ArH), 7.27 (d, JZ7.2 Hz, 2H, ArH), 7.28–7.35
(m, 5H, ArH), 7.38 (dd, JZ1.6, 6.8 Hz, 2H, ArH). 13C NMR
(CDCl3) d: 46.0 (CH2), 69.7 (CH2), 99.8 (CH), 103.5 (CH),
106.4 (CH), 126.2 (CH), 126.8 (CH), 127.4 (CH), 127.4
(CH), 127.7 (CH), 128.4 (CH), 128.5 (CH), 129.9 (CH),
131.4 (CH), 136.7 (C), 137.2 (C), 149.3 (C), 160.0 (C). EI-
MS m/z: 315 (MC), 288, 271, 239, 224, 207, 196, 182, 146,
117, 115, 91, 77. HR-MS calcd for C22H21NO 315.1623,
found 315.1625.
NH), 5.04 (d, JZ6.0 Hz, 1H, CH), 6.34 (dd, JZ6.0,
15.6 Hz, 1H, CH), 6.58 (d, JZ15.6 Hz, 1H, ArH), 6.59 (dd,
JZ0.8, 8.8 Hz, 2H, CH, ArH), 6.67 (ddt, JZ0.8, 1.2,
7.2 Hz, 1H, ArH), 7.07–7.40 (m, 12H, ArH). 13C NMR
(CDCl3) d: 60.5 (CH), 113.5 (CH), 117.6 (CH), 126.4 (CH),
127.1 (CH), 127.4 (CH), 127.6 (CH), 128.5 (CH), 128.7
(CH), 129.1 (CH), 130.6 (CH), 131.0 (CH), 136.6 (C), 142.0
(C), 147.1 (C). EI-MS m/z: 285 (MC), 270, 206, 193, 178,
165, 152, 115, 91, 77, 65. HR-MS calcd for C21H19N
285.1517, found 285.1514.
4.2.24. N-(2-Methylprop-2-enyl)aniline (8).30 Deep brown
oil. IR (KBr) n: 3419 cmK1. 1H NMR (CDCl3) d: 1.77 (s, 3H,
CH3), 3.66 (s, 2H, CH2), 3.80 (br s, 1H, NH), 4.86–4.89 (m,
1H, vinyl H), 4.95–4.98 (m, 1H, vinyl H), 6.60 (d, JZ8.0 Hz,
2H, ArH), 6.69 (t, JZ7.2 Hz, 1H, ArH), 7.16 (dd, JZ7.2,
8.0 Hz, 2H, ArH). 13C NMR (CDCl3) d: 20.4 (CH3), 49.9
(CH2), 110.9 (CH2), 112.8 (CH), 117.3 (CH), 129.1 (CH),
142.7 (C), 148.2 (C). EI-MS m/z: 147 (MC), 132, 118, 106,
91, 77. HR-MS calcd for C10H13N 147.1048, found 147.1045.
4.2.20. N,N-Dicinnamyl-3-benzyloxyaniline (4o). Brown
crystals. Mp 73–74 8C (chloroform/hexane).1H NMR
(CDCl3) d: 4.10 (dd, JZ1.2, 5.6 Hz, 4H, CH2!2), 5.03
(s, 2H, CH2), 6.25 (dt, JZ5.6, 16.0 Hz, 2H, vinyl H), 6.37
(d, JZ8.0 Hz, 1H, ArH), 6.42–6.49 (m, 2H, ArH), 6.52 (d,
JZ16.0 Hz, 2H, vinyl H), 7.11–7.24 (m, 4H, ArH), 7.28–
7.33 (m, 2H, ArH), 7.29 (dd, JZ6.8, 8.0 Hz, 4H, ArH), 7.35
(dd, JZ1.6, 7.2 Hz, 4H, ArH), 7.41 (dd, JZ1.6, 6.8 Hz, 2H,
ArH). 13C NMR (CDCl3) d: 52.2 (CH2), 69.9 (CH2), 100.0
(CH), 102.4 (CH), 105.9 (CH), 125.7 (CH), 126.4 (CH),
127.4 (CH), 127.5 (CH), 127.8 (CH), 128.3 (CH), 128.5
(CH), 129.9 (CH), 131.3 (CH), 136.8 (C), 137.3 (C), 150.2
(C), 160.1 (C). EI-MS m/z: 431 (MC), 401, 355, 340, 327,
4.2.25. N,N-Bis(2-methylprop-2-enyl)aniline (9). Deep
blue oil. H NMR (CDCl3) d: 1.74 (s, 6H, CH3!2), 3.80
1
(s, 4H, CH2!2), 4.81 (d, JZ24.8 Hz, 4H, CH2!2), 6.62 (d,
JZ8.8 Hz, 2H, ArH), 6.66 (d, JZ7.2 Hz, 1H, ArH), 7.17
(dd, JZ7.6, 8.0 Hz, 2H, ArH). 13C NMR (CDCl3) d: 20.0
(CH3), 56.3 (CH2), 110.2 (CH2), 111.9 (CH), 115.9 (CH),
128.8 (CH), 140.5 (C), 148.7 (C). EI-MS m/z: 201 (MC),

S.-C. Yang et al. / Tetrahedron 62 (2006) 3949–3958
3957
Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 2753–2763. (e)
Brunet, J.; Commenges, G.; Neibecker, D.; Philippot, K.
J. Organomet. Chem. 1994, 469, 221–228.
186, 160, 145, 130, 118, 104, 91, 77. HR-MS calcd for
C14H19N 201.1518, found 201.1517.
2. Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G.
Principles and Applications of Organotransition Metal
Chemistry; University Science Books: Mill Valley, CA, 1987.
4.2.26. N-(2-Chloroallyl)aniline (10). Deep brown oil. IR
(KBr) n: 3418 cmK1. 1H NMR (CDCl3) d: 3.88 (dd, JZ1.2,
1.2 Hz, 2H, CH2), 4.03 (br s, 1H, NH), 5.29 (dt, JZ1.2,
2.8 Hz, 1H, vinyl H), 5.39 (dt, JZ1.6, 2.8 Hz, 1H, vinyl H),
6.58 (dd, JZ0.8, 8.4 Hz, 2H, ArH), 6.73 (ddt, JZ0.8, 1.2,
7.6 Hz, 1H, ArH), 7.17 (dd, JZ7.6, 8.4 Hz, 2H, ArH). 13C
NMR (CDCl3) d: 50.0 (CH2), 112.4 (CH2), 112.9 (CH),
118.1 (CH), 129.2 (CH), 139.2 (C), 146.7 (C). EI-MS m/z:
169 (MCC2), 167 (MC), 132, 118, 106, 92, 77. HR-MS
calcd for C9H10ClN 167.0502, found 167.0503.
˚
3. (a) Connell, R. D.; Rein, T.; Akermark, B.; Helquist, P. J. Org.
Chem. 1988, 53, 3845–3849. (b) Sakamoto, M.; Shimizu, I.;
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Kawase, T.; Morimoto, T.; Kakiuchi, K. Organometallics
2003, 22, 2996–2999.
4. (a) Goldeski, S. A. In Nucleophiles with Allyl–Metal
Complexes; Trost, B. M., Fleming, I., Eds.; Comprehensive
Organic Synthesis; Pergamon: New York, 1991; Vol. 4;
Chapter 3.3. (b) Harrington, P. J. In Transition Metal Allyl
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E. W., Stone, F. G. A., Wilkinson, G., Eds.; Comprehensive
Organometallic Chemistry II; Pergamon: New York, 1995;
Vol. 12; Chapter 8.2. (c) Tsuji, J. Palladium Reagents and
Catalysts; Wiley: New York, 1995.
4.2.27. N-(2-Cyclohexenyl)aniline (11). Light brown oil. IR
(KBr) n: 3407 cmK1. 1H NMR (CDCl3) d: 1.57–1.74 (m, 3H,
CH2), 1.86–1.92 (m, 1H, CH2), 1.99–2.05 (m, 2H, CH2), 3.57
(br s, 1H, NH), 3.94–4.01 (m, 1H, CH), 5.74 (ddt, JZ2.4, 2.4,
10.0 Hz, 1H, vinyl H), 5.83 (ddt, JZ1.6, 3.6, 10.0 Hz, 1H,
vinyl H), 6.60 (d, JZ8.4 Hz, 2H, ArH), 6.67 (dt, JZ0.8,
7.2 Hz, 1H, ArH), 7.12–7.18 (m, 2H, ArH). 13C NMR
(CDCl3) d: 19.6 (CH2), 25.1 (CH2), 28.8 (CH2), 47.8 (CH),
113.2 (CH), 117.1 (CH), 128.5 (CH), 129.2 (CH), 130.0
(CH), 147.1 (C). EI-MS m/z: 173 (MC), 145, 144, 130, 96.
HR-MS calcd for C12H15N 173.1205, found 173.1203.
5. (a) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1989, 28,
1173–1192. (b) Oppolzer, W. Angew. Chem., Int. Ed. Engl.
1989, 28, 38–52. (c) Tsuji, J. Synthesis 1990, 739–749. (d)
Trost, B. M. Pure Appl. Chem. 1992, 64, 315–322. (e)
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4.2.28. N-(3-Methylbut-2-enyl)aniline (14). Brown oil. IR
1
(KBr) n: 3408 cmK1. H NMR (CDCl3) d: 1.71 (s, 3H,
CH3), 1.74 (s, 3H, CH3), 3.60 (br s, 1H, NH), 3.68 (d, JZ
6.8 Hz, 2H, CH2), 5.30–5.35 (m, 1H, vinyl H), 6.61 (dd, JZ
1.2, 8.4 Hz, 2H, ArH), 6.70 (ddd, JZ0.8, 1.2, 7.2 Hz, 1H,
ArH), 7.17 (dd, JZ7.2, 8.4 Hz, 2H, ArH). 13C NMR
(CDCl3) d: 17.9 (CH3), 25.7 (CH3), 42.0 (CH2), 112.9 (CH),
117.3 (CH), 121.6 (C), 129.1 (C), 135.6 (C), 148.4 (C). EI-
MS m/z: 161 (MC), 146, 144, 130, 118, 106, 93, 77. HR-MS
calcd for C11H15N 161.1205, found 161.1204.
6. (a) Stary, I.; Kocovsky, P. J. Am. Chem. Soc. 1989, 111,
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4.2.29. N-(1,1-Dimethylprop-2-enyl)aniline (15). Brown
1
oil. IR (KBr) n: 3421 cmK1. H NMR (CDCl3) d: 1.38 (s,
6H, CH3!2), 3.52 (br s, 1H, NH), 5.10 (dd, JZ1.2,
10.8 Hz, 1H, vinyl H), 5.18 (dd, JZ1.2, 17.6 Hz, 1H, vinyl
H), 6.01 (dd, JZ10.8, 17.6 Hz, 1H, vinylH), 6.66–6.70 (m,
1H, ArH), 6.69 (dd, JZ1.2, 7.6 Hz, 2H, ArH), 7.10 (dd, JZ
7.6, 8.4 Hz, 2H, ArH). 13C NMR (CDCl3) d: 28.3 (CH3),
54.6 (CH), 112.7 (CH2), 115.7 (CH), 117.4 (CH), 128.7
(CH), 146.1 (CH), 146.6 (C). EI-MS m/z: 161 (MC), 146,
131, 130, 120, 118, 103, 93, 91, 77. HR-MS calcd For
C11H15N 161.1205, found 161.1207.
7. (a) Minami, I.; Ohashi, Y.; Shimizu, I.; Tsuji, J. Tetrahedron
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Acknowledgements
9. Imidoesters: (a) Schenck, T. G.; Bosnich, B. J. Am. Chem. Soc.
1985, 107, 2058–2066. Xanthates: (b) Auburn, P. R.;
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We gratefully acknowledge the National Science Council of
the Republic of China for financial support.
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