Metal-free synthesis of allylic amines by cross-dehydrogenative-coupling of 1,3-diarylpropenes with anilines and amides under mild conditions

Article abstract of DOI:10.1039/c2ob06826e

Dehydrogenative cross-coupling reaction of primary anilines, secondary anilines, carboxamides, and sulfonamides with 1,3-diarylpropenes to form a series of allylic amines promoted by DDQ have been realized. Both monoallylation and diallylation products can be selectively synthesized when primary anilines are used as the starting materials. The method may provide a wide scope of allylamines in scientific research including biologically active compound library construction.

Full text of DOI:10.1039/c2ob06826e

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PAPER
Metal-free synthesis of allylic amines by cross-dehydrogenative-coupling of
1,3-diarylpropenes with anilines and amides under mild conditions†
Zhiming Wang,a,b Hanjie Mo,a Dongping Chenga,c and Weiliang Bao*a
Received 31st October 2011, Accepted 11th January 2012
DOI: 10.1039/c2ob06826e
Dehydrogenative cross-coupling reaction of primary anilines, secondary anilines, carboxamides, and
sulfonamides with 1,3-diarylpropenes to form a series of allylic amines promoted by DDQ have been
realized. Both monoallylation and diallylation products can be selectively synthesized when primary
anilines are used as the starting materials. The method may provide a wide scope of allylamines in
scientific research including biologically active compound library construction.
Allylic amines are ubiquitous in various biologically active com-
pounds,1 such as the antifungal drug Naftifine2 and the calcium
channel blocker Flunarizine,3 and are highly useful substrates for
many types of reactions, such as asymmetric isomerization4 and
ring-closing metathesis.5 The synthesis of allylic amines usually
employs activated allylic compounds, in particular, allylic
halides, carboxylates, and carbonates, because of the strong
activity of these substrates.6 But the use of such activated sub-
strates causes the formation of more than stoichiometric amounts
of unwanted chemical waste. Then allylic alcohols were used to
react with amines to synthesize allylic amines.7–14 However,
most of the reactions required rather severe catalytic reaction
conditions and transition metal-based protocols usually have
some inherent limitations such as moisture sensitivity, costly
metal catalysts and environmental toxicity. Also, because of the
higher nucleophilicity of the monoallylation products, the reac-
tion always results both in the formations of monoallylation pro-
ducts and diallylation products.
cross-dehydrogenative coupling (CDC) has been rarely realized.
In 2010, Armstrong and his coworkers reported a copper-cata-
lyzed oxidative amination reaction of azoles on 2-position to
form a C–N bond using secondary amines with or without elec-
tron withdrawing-groups.18 In 2010, Wang and his coworkers
reported a copper-catalyzed synthesis of polysubstituted oxazoles
using benzylamines and 1,3-dicarbonyl derivatives as the sub-
strates. They used iodine as the additive to pre-activate the sub-
strates, and proposed that ethyl 2-iodo-3-oxobutanoate may be a
key intermediate.19 The amination of sp3 C–H bonds using
primary amines without any additives remains a challenge.
In the past few years, our group reported metal-free coupling
reactions to form new C–C, C–O and C–S bonds directly using
1,3-diarylpropenes promoted by DDQ.20 Also, in 2009, we
reported a Pd-catalyzed indolation reaction of allylic compounds
with DDQ.21 Herein, we report a metal-free coupling reaction to
synthesize both monoallylamines and diallylamines directly
using allylic sp3 C–H bonds and anilines or amides promoted by
DDQ under very mild conditions.
To begin our study, we chose 1,3-diphenylpropene 1a and
aniline 2a as the standard substrates to search for suitable reac-
tion conditions. Firstly, we mixed two substrates in CH2Cl2 at
0 °C, then a stoichiometric amount of DDQ was added, no
desired coupling product was detected. Because aniline pos-
sesses strong activity and it’s easily oxidized by DDQ, we
changed the addition sequence of the substrates. To a solution of
1,3-diarylpropene in 2 mL CH2Cl2, DDQ was added at 0 °C.
After stirring for about 5–10 minutes, aniline was injected into
the mixture slowly. The reaction finished in about 10 minutes,
and the coupling product N-(1,3-diphenylallyl)aniline 3a was
obtained in 51% yield and N,N-bis(1,3-diphenylallyl)aniline 4a
in 37% yield (Table 1, entry 1). The conversion rate of 1,3-
diphenylpropene (1a) was 88%, but the monoallylation or dially-
lation selectivities were not satisfactory. Then the reaction was
carried out under different temperatures (Table 1, entries 2–5).
When the temperature was increased to 50 °C, the molar ratio of
With the prevalence of “atom economy”15 and “green chem-
istry”,16 the cross-coupling reaction to construct allylic amines
directly using allylic sp3 C–H bond and amines has attracted
great interest. Amination reactions of different C–H bonds to
form new C–N bonds have been reported by many groups.
However, most of the substrates in the amination reactions were
amide, sulfonamide or anilines with strong electron withdraw-
ing-groups.17 Reactions of amines without any electron with-
drawing-groups with C–H bonds to form new C–N bonds via
aDepartment of Chemistry, Zhejiang University (Xixi Campus),
Hangzhou, Zhejiang 310028, China. E-mail: wlbao@css.zju.edu.cn
bSchool of Petrochemical Engineering, Changzhou University,
Changzhou, Jiangsu 213164, China
cCollege of Pharmaceutical Science, Zhejiang University of Technology,
Hangzhou 310014, Zhejiang, China
†Electronic supplementary information (ESI) available: 1H and 13C
NMR spectra copies of compounds 3, 4 and 6. See DOI: 10.1039/
c2ob06826e
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Table 1 Optimization of the CDC reaction conditionsa
Table 2 The CDC reaction of 1,3-diarylpropenes with primary
anilinesa,b
Yieldb (%)
3a
Entry
Temp (°C)
Solvent
4a
1
2
3
4
5
6
7
8
0
r.t.
50
−15
−40
0
0
0
0
0
0
0
0
r.t.
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CHCl3
51
25
3
55
52
55
52
37
46
30
15
Trace
85
90
37
50
45
21
7
30
33
20
15
11
DCE
Toluene
CH3CN
CH3NO2
DMF
Cyclohexane
THF
9
10
11
12
13
14
Trace
Trace
3
1,4-Dioxane
<1
a 0.5 mmol of 1a, 0.55 mmol of 2a, 0.55 mmol of DDQ, 2 mL of
solvent, 10 min. b Isolated yield.
two products was 1 : 15 (3a : 4a), although the conversion rate of
the substrate (1a) was only 48% (Table 1, entry 3). When the
reaction temperature was lowered to −40 °C, the molar ratio of
two products was 7 : 1 (3a : 4a), the yield of 3a was only 52%,
and this result was not satisfactory (Table 1, entry 5). Then a
number of solvents were screened. When CHCl3 and DCE were
used as the solvent, the results were similar to the result when
CH2Cl2 was used as the solvent (Table 1, entries 6, 7). When
toluene, CH3CN and CH3NO2 were used as the solvent, the con-
version rate of 1a was moderate and the monoallylation selectiv-
ity of aniline was still not satisfactory (Table 1, entries 8, 9, 10).
When DMF was used as the solvent, we obtained the monoally-
lation product 3a in 15% yield, and product 4a was not detected
(Table 1, entry 11). When cyclohexane was used, no products
were obtained because of the poor solubility of DDQ in cyclo-
hexane (Table 1, entry 12). When THF was used as the solvent,
the products 3a and 4a were obtained in 85% and 3% yield
respectively, the molar ratio of two products was 28 : 1 (Table 1,
entry 13). Surprisingly, when 1,4-dioxane was used as the
solvent and the reaction was carried out at room temperature, the
monoallylation product 3a was obtained in 90% yield and only
less than 1% yield of 4a was gathered (Table 1, entry 14).
With the optimized reaction conditions established, various
substrates were subjected to the CDC reactions and representa-
tive results are summarized in Table 2. Anilines with electron
withdrawing-groups reacted well with the diarylpropenes under
the standard reaction condition (Table 2, 3b–3c, 3f and 3h–3k).
When anilines with electron donating-groups were used as the
substrates, the yield of desired monoallylation product decreased
slightly and was also satisfactory (Table 2, 3l–3o). Unfortunately,
when aliphatic amines were used as the substrates, no desired
coupling products were detected. When 1,3-diarylpropene with
electron withdrawing-groups on the aromatic ring was used, the
a 0.5 mmol of 1, 0.55 mmol of 2, 0.55 mmol of DDQ, 2 mL of 1,4-
dioxane, r.t., 10 min. b Isolated yield.
yield of the coupling product was decreased a little but still satis-
factory (Table 2, 3p). To expand the scope of the substrates, we
further examined the unsymmetrical 1,3-diarylpropenes and
obtained the expected products with poor regioselectivities
according to the 1H NMR and 13C NMR (Table 2, 3q–3x).
When 1-methyl-1,3-diarylpropene was used, only less than 3%
4250 | Org. Biomol. Chem., 2012, 10, 4249–4255
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Table 3 The CDC reaction of 1,3-diarylpropenes with secondary
anilines and amidesab
Scheme 1 A possible mechanism.
On the basis of the literature and the experimental obser-
vations, a plausible mechanism is proposed in Scheme 1. The
CDC reaction may follow two pathways: hydride transferred
directly from the allylic position to DDQ and/or proton abstrac-
tion after an electron was transferred from the allylic double
bond to DDQ.20,22 In our experiment, when the 1,3-diphenylpro-
pene was treated with aniline, we observed the self-
coupling product of 1,3-diphenylpropene. This coupling product
may indicate
a single-electron transfer in the reaction.
Rearranged products 3q–3x and 6i–6j were also obtained in the
experiments. Therefore, an allylic cation may also be involved in
the coupling process. These results may support our proposed
mechanism.
In summary, we have developed a new method to synthesize
allylic amines via CDC reaction between 1,3-diarylpropenes and
anilines or amides promoted by DDQ. The methodology is
highly facile and efficient, and may provide a wide scope of
allylic amines in scientific research and access to more biologi-
cally active compounds library.
a 0.5 mmol of 1, 0.55 mmol of 5, 0.55 mmol of DDQ, 2 mL of 1,4-
dioxane, r.t. 10 min. b Isolated yield. c Nitromethane was used as a
solvent instead of 1,4-dioxane.
yield of the coupling product was gathered, the steric effect may
largely interfere with the reaction.
Experimental
Then a series of secondary anilines and amides were used as
substrates. Under the same reaction condition, a number of coup-
ling products were also obtained in good yield, and representa-
tive results are summarized in Table 3. When N-methylaniline
(5a) was used, the coupling product 6a was obtained in 81%
yield. A series of N,N-diarylamines were used as substrates to
undergo the CDC reaction to form more stable coupling pro-
ducts. When an N,N-diarylamine with electron withdrawing-
group on the aromatic ring was used, the desired product was
obtained in high yield (Table 3, 6c). When N,N-diarylamines
with electron donating-groups on the aromatic rings were exam-
ined, the yields of the coupling products decreased a little
(Table 3, 6d, 6e, 6f, 6g, 6h). Then 1-bromo-4-(3-phenylprop-1-
enyl)benzene (1b) was used as the substrate, isomers 6i and 6j
were obtained, and the yield of the products was moderate. Inter-
estingly, when benzamide, acrylamide, pyrrolidin-2-one and p-
toluene sulfonamide were used as the starting materials, the
coupling reaction took place smoothly with good to excellent
reaction yields (Table 3, 6k–6n).
All 1H NMR (400 MHz) and 13C MNR (100 MHz) spectra were
recorded in CDCl3 using TMS as an internal standard. The start-
ing materials diarylpropenes23 and N,N-diarylamines24 were pre-
pared according to the literature procedures.
General procedure for the preparation of compounds 3a–3x and
6a–6j
To a mixture of 1,3-diarylpropene (0.5 mmol) and 2 mL of 1,4-
dioxane, DDQ 123 mg (0.55 mmol) was added at room tempera-
ture. After stirring for about 5–10 minutes, aniline (0.55 mmol)
was dissolved in 1 mL of 1,4-dioxane, and dropped into the
mixture slowly. Then the reaction vessel was capped and the
mixture stirred for 10 minutes. The resulting mixture was
purified by flash column chromatography on silica gel (pet-
roleum ether–ethyl acetate) to give the desired pure product
(3a–3x or 6a–6j).
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General procedure for the preparation of compounds 6k–6n
6.38 (dd, J = 6.4, 15.6 Hz, 1H), 5.06 (d, J = 6.0 Hz, 1H), 4.17
(s, 1H); 13C NMR (100 MHz, CDCl3): δ = 67.0, 112.0, 126.1,
126.5, 127.0, 128.0, 128.1, 128.5, 128.6, 129.1, 132.2, 135.9,
138.4, 140.2, 152.0; IR (neat): 3375, 3028, 2916, 1595, 1499,
1470, 1301, 1184, 1109, 1027, 967, 908, 833, 798, 747,
696 cm−1; MS (70 eV, EI) m/z = 330; HRMS (EI): m/z calcd for
C21H18N2O2 (M+): 330.1368, Found 330.1371.
(E)-N-(1,3-Diphenylallyl)-3,5-dimethylaniline (3g): light
yellow oil; 81% yield; 1H NMR (400 MHz, CDCl3): δ =
7.49–7.26 (m, 11H), 6.68 (d, J = 8.4 Hz, 1H), 6.48–6.41 (m,
2H), 6.34 (s, 2H), 5.13 (d, J = 6.4 Hz, 1H), 4.05 (s, 1H), 2.26 (s,
6H); 13C NMR (100 MHz, CDCl3): δ = 21.5, 60.5, 111.4, 119.7,
126.5, 127.2, 127.4, 127.5, 128.5, 128.7, 130.8, 130.9, 136.7,
138.8, 142.3, 147.4; IR (neat): 3405, 3025, 2915, 2856, 1599,
1509, 1493, 1449, 1336, 1183, 967, 822, 746, 693 cm−1; MS
(70 eV, EI) m/z = 313; HRMS (EI): m/z calcd for C23H23N (M+):
313.1830, Found 313.1827.
To a 10 mL two-necked round-bottom flask with a mixture of
carboxamide or sulfonamide (0.5 mmol) and diarylallylic com-
pound (0.6 mmol) in MeNO2 (3 mL), DDQ (0.6 mmol) was
added under N2. The resulting mixture was stirred for 6 h at
50 °C. The resulting mixture was purified by flash column
chromatography on silica gel (petroleum ether–ethyl acetate) to
give the desired pure product (6k–6n).
(E)-N-(1,3-Diphenylallyl)aniline (3a)25: light yellow oil;
90% yield; 1H NMR (400 MHz, CDCl3): δ = 7.47–7.14 (m,
13H), 6.73 (t, J = 7.2 Hz, 1H), 6.67–6.62 (m, 3H), 6.41 (dd, J =
6.4, 16 Hz, 1H), 5.11 (d, J = 6.4 Hz, 1H), 4.14 (s, 1H); 13C
NMR (100 MHz, CDCl3): δ = 60.6, 113.5, 117.6, 126.4, 127.1,
127.4, 127.6, 128.5, 128.8, 129.1, 130.7, 131.0, 136.6, 142.0,
147.2; IR (neat): 3421, 3026, 2838, 1600, 1491, 1450, 1307,
1251, 1158, 1129, 967, 810, 746, 696 cm−1; MS (70 eV, EI)
m/z = 285.
(E)-N-(1,3-Diphenylallyl)-2-nitroaniline (3h): light yellow
(3b)26:
light
1
(E)-4-Chloro-N-(1,3-diphenylallyl)aniline
oil; 95% yield; H NMR (400 MHz, CDCl3): δ = 8.50 (d, J =
yellow oil; 91% yield; 1H NMR (400 MHz, CDCl3): δ =
7.45–7.25 (m, 11H), 7.10 (d, J = 8.4 Hz, 2H), 6.65–6.55 (m,
3H), 6.40 (dd, J = 6.0, 16.0 Hz, 1H), 5.06 (d, J = 6.4 Hz, 1H),
4.16 (s, 1H); 13C NMR (100 MHz, CDCl3): δ = 60.7, 114.6,
122.3, 126.5, 127.1, 127.7, 127.8, 128.5, 128.8, 128.9, 130.2,
131.3, 136.4, 141.5, 145.7; IR (neat): 3412, 3027, 2852, 1597,
5.6 Hz, 1H), 8.19 (d, J = 8.0 Hz, 1H), 7.43–7.23 (m, 11H), 6.82
(d, J = 8.4 Hz, 1H), 6.67–6.58 (m, 2H), 6.41 (dd, J = 6.4, 15.6
Hz, 1H), 5.31 (s, 1H); 13C NMR (100 MHz, CDCl3): δ = 67.0,
115.0, 115.9, 126.6, 126.7, 126.9, 127.9, 128.0, 128.6, 128.9,
129.1, 131.8, 132.4, 136.0, 140.4, 144.1; IR (neat): 3376, 3028,
2855, 1614, 1572, 1500, 1417, 1349, 1259, 1233, 1150, 1038,
966, 872, 740, 693 cm−1; MS (70 eV, EI) m/z = 330; HRMS
(EI): m/z calcd for C21H18N2O2 (M+): 330.1368, Found
330.1370.
1493, 1450, 1313, 1258, 1177, 1122, 967, 814, 745, 696 cm−1
MS (70 eV, EI) m/z = 319.
;
(E)-4-Bromo-N-(1,3-diphenylallyl)aniline (3c): light yellow
1
oil; 92% yield; H NMR (400 MHz, CDCl3): δ = 7.44–7.22 (m,
(E)-N-(1,3-Diphenylallyl)-3-(trifluoromethyl)aniline (3i):
1
13H), 6.62 (d, J = 16.0 Hz, 1H), 6.52 (d, J = 6.8 Hz, 2H), 6.38
(dd, J = 6.4, 15.6 Hz, 1H), 5.06 (d, J = 6.0 Hz, 1H), 4.17 (s,
1H); 13C NMR (100 MHz, CDCl3): δ = 60.5, 109.3, 115.1,
126.4, 127.1, 127.6, 127.7, 128.5, 128.8, 130.0, 131.3, 131.8,
136.4, 141.4, 146.0; IR (neat): 3411, 3026, 2862, 1593, 1492,
light yellow oil; 93% yield; H NMR (400 MHz, CDCl3): δ =
7.44–7.19 (m, 11H), 6.94 (d, J = 7.6 Hz, 1H), 6.87 (s, 1H), 6.75
(d, J = 8.0 Hz, 1H), 6.64 (d, J = 16.0 Hz, 1H), 6.38 (dd, J = 5.6,
16.0 Hz, 1H), 5.11 (d, J = 6.0 Hz, 1H), 4.31 (s, 1H); 13C NMR
(100 MHz, CDCl3): δ = 60.4, 110.1, 114.1, 116.2, 126.5, 127.1,
127.7, 127.8, 128.5, 128.9, 129.6, 129.8, 131.5, 136.4, 141.3,
147.2; IR (neat): 3412, 3027, 2972, 2916, 1614, 1511, 1340,
1163, 1118, 1067, 1028, 911, 865, 783, 744, 695 cm−1; MS (70
eV, EI) m/z = 353; HRMS (EI): m/z calcd for C22H18F3N (M+):
353.1391, Found 353.1392.
(E)-N-(1,3-Diphenylallyl)-2,4-difluoroaniline (3j): light
yellow oil; 82% yield; 1H NMR (400 MHz, CDCl3): δ =
7.46–7.25 (m, 10H), 6.84–6.78 (m, 1H), 6.67–6.57 (m, 3H),
6.41 (dd, J = 6.0, 15.6 Hz, 1H), 5.06 (d, J = 6.0 Hz, 1H), 4.23
(s, 1H); 13C NMR (100 MHz, CDCl3): δ = 60.8, 103.3, 110.5,
113.4, 126.5, 127.0, 127.7, 127.8, 128.5, 128.9, 130.1, 131.3,
132.0, 132.1, 136.3, 141.4, 149.6, 152.0, 153.2; IR (neat): 3425,
3028, 1601, 1515, 1427, 1337, 1267, 1205, 1141, 1093, 962,
848, 796, 747, 697 cm−1; MS (70 eV, EI) m/z = 321; HRMS
(EI): m/z calcd for C21H17F2N (M+): 321.1329, Found 321.1327.
1450, 1395, 1314, 1258, 1178, 1123, 968, 812, 746, 697 cm−1
;
MS (70 eV, EI) m/z = 363; HRMS (EI): m/z calcd for
C21H18BrN (M+): 363.0623, Found 363.0625.
(E)-N-(1,3-Diphenylallyl)-4-methylaniline (3d)26: light
yellow oil; 85% yield; 1H NMR (400 MHz, CDCl3): δ =
7.49–7.26 (m, 11H), 7.00 (d, J = 8.0 Hz, 2H), 6.69–6.59 (m,
3H), 6.44 (dd, J = 6.4, 16.0 Hz, 1H), 5.10 (d, J = 6.0 Hz, 1H),
4.04 (s, 1H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
20.3, 60.9, 113.7, 126.5, 126.9, 127.2, 127.4, 127.6, 128.5,
128.7, 129.6, 130.8, 130.9, 136.7, 142.2, 145.0; IR (neat): 3406,
2916, 2862, 1615, 1515, 1450, 1402, 1300, 1258, 1182, 1127,
1069, 1028, 967, 807, 744, 696 cm−1; MS (70 eV, EI) m/z =
299.
(E)-N-(1,3-Diphenylallyl)-4-methoxyaniline (3e)27: light
yellow oil; 77% yield; 1H NMR (400 MHz, CDCl3): δ =
7.47–7.24 (m, 11H), 6.78–6.75 (m, 2H), 6.67–6.61 (m, 3H),
6.41 (dd, J = 6.4, 16.4 Hz, 1H), 5.03 (d, J = 6.4 Hz, 1H), 3.92
(s, 1H), 3.74 (s, 1H); 13C NMR (100 MHz, CDCl3): δ = 55.7,
67.0, 114.7, 114.9, 126.4, 127.1, 127.4, 127.5, 128.5, 128.7,
130.8, 131.1, 136.6, 141.4, 142.3, 152.2; IR (neat): 3397, 2949,
2831, 1599, 1509, 1450, 1295, 1236, 1179, 1121, 1035, 968,
914, 819, 745, 697 cm−1; MS (70 eV, EI) m/z = 315.
(E)-1-(4-(1,3-Diphenylallylamino)phenyl)ethanone
(3k):
1
light yellow oil; 90% yield; H NMR (400 MHz, CDCl3): δ =
7.79 (d, J = 8.8 Hz, 2H), 7.43–7.24 (m, 11H), 6.63–6.58 (m,
3H), 6.38 (dd, J = 6.4, 16.0 Hz, 1H), 5.19 (s, 1H), 4.23 (s, 1H);
13C NMR (100 MHz, CDCl3): δ = 25.9, 67.0, 112.3, 126.5,
127.1, 127.8, 127.9, 128.5, 128.9, 129.3, 130.6, 131.7, 136.2,
140.9, 150.9, 196.3; IR (neat): 3344, 3027, 1656, 1593, 1524,
1488, 1356, 1275, 1179, 962, 911, 827, 743, 698 cm−1; MS (70
eV, EI) m/z = 327; HRMS (EI): m/z calcd for C23H21NO (M+):
327.1623, Found, 327.1627.
(E)-N-(1,3-Diphenylallyl)-4-nitroaniline (3f): light yellow
1
solid; 97% yield; H NMR (400 MHz, CDCl3): δ = 7.44–7.22
(m, 13H), 6.62 (d, J = 16.0 Hz, 1H), 6.52 (d, J = 9.2 Hz, 2H),
4252 | Org. Biomol. Chem., 2012, 10, 4249–4255
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(E)-N-(1,3-Diphenylallyl)quinolin-6-amine (3l): light yellow
oil; 88% yield; H NMR (400 MHz, CDCl3): δ = 8.62 (d, J = 4
126.5, 127.2, 127.6, 127.7, 127.8, 128.4, 128.5, 128.6, 128.8,
128.9, 129.1, 129.2, 129.7, 130.1, 131.3, 131.6, 133.1, 133.2,
135.1, 136.3, 140.5, 141.8, 146.8, 147.1; IR (neat): 3411, 3026,
2926, 1600, 1497, 1450, 1427, 1404, 1314, 1260, 1091, 1012,
968, 908, 823, 748, 695 cm−1; MS (70 eV, EI) m/z = 363;
HRMS (EI): m/z calcd for C21H18BrN (M+): 363.0623, Found
363.0625.
(E)-N-(3-(2-Chlorophenyl)-1-phenylallyl)benzenamine (3s)
and (E)-N-(1-(2- chlorophenyl)-3-phenylallyl)benzenamine
(3t): light yellow oil; 77% yield; 1H NMR (400 MHz, CDCl3): δ
= 7.52–7.11 (m, 29H), 6.71–6.56 (m, 8.5H), 6.38–6.33 (m,
2.5H), 5.53 (br, 1.5H), 5.12 (d, J = 6.0 Hz, 1H), 4.19–4.13 (br,
2.5H); 13C NMR (100 MHz, CDCl3): δ = 56.9, 60.8, 113.5,
113.7, 117.8, 117.9, 126.6, 126.8, 127.0, 127.2, 127.3, 127.5,
127.6, 127.8, 128.2, 128.6, 128.7, 128.9, 129.1, 129.2, 129.7,
129.9, 131.9, 133.2, 133.4, 133.7, 135.0, 136.5, 139.2, 141.8;
MS (70 eV, EI) m/z = 319; HRMS (EI): m/z calcd for
C21H18ClN (M+): 319.1128, Found 319.1126.
(E)-N-(1-Phenyl-3-o-tolylallyl)benzenamine (3u) and (E)-
N-(3-phenyl-1-o-tolylallyl)benzenamine (3v): light yellow oil;
69% yield; 1H NMR (400 MHz, CDCl3): δ = 7.49–7.31 (m,
11H), 7.26–7.16 (m, 11H), 6.88 (d, J = 15.6 Hz, 1H), 6.74–6.68
(m, 4H), 6.63–6.60 (m, 3H), 6.44 (dd, J = 15.6, 5.6 Hz, 1H),
6.28 (dd, J = 16.0, 6.4 Hz, 1H), 5.27 (d, J = 5.6 Hz, 1H), 5.14
(d, J = 6.4 Hz, 1H), 4.13–4.08 (br, 2H), 2.44 (s, 3H), 2.30 (s,
3H); 13C NMR (100 MHz, CDCl3): δ = 19.3, 19.7, 56.9, 60.9,
113.2, 113.7, 117.6, 117.7, 125.8, 126.0, 126.4, 126.5, 126.7,
127.2, 127.4, 127.51, 127.56, 127.6, 128.6, 128.8, 129.1, 129.2,
129.3, 129.8, 130.2, 130.8, 131.3, 132.0, 135.6, 135.9, 136.0,
136.7, 139.8, 142.2, 147.2, 147.4; MS (70 eV, EI) m/z = 299;
HRMS (EI): m/z calcd for C22H21N (M+): 299.1674, Found
299.1675.
(E)-N-(3-(4-Chlorophenyl)-1-phenylallyl)benzenamine
(3w) and (E)-N-(1-(4- chlorophenyl)-3-phenylallyl)benzena-
mine (3x): light yellow oil; 72% yield; 1H NMR (400 MHz,
CDCl3): δ = 7.46–7.23 (m, 8H), 7.16–7.12 (m, 2H), 6.96–6.87
(m, 1H), 6.73–6.71 (m, 1H), 6.63–6.55 (m, 3H), 6.39–6.31 (m,
1H), 5.06 (dd, J = 10.0, 4.8 Hz, 1H), 4.09 (br, 1H); 13C NMR
(100 MHz, CDCl3): δ = 60.1, 60.6, 113.5, 113.6, 117.8, 118.0,
120.7, 126.5, 127.2, 127.5, 127.6, 127.7, 127.9, 128.5, 128.6,
128.7, 128.8, 128.9, 129.0, 129.1, 129.2, 129.8, 130.1, 130.7,
131.4, 131.6, 133.2, 133.3, 135.1, 136.4, 140.6, 141.8, 146.9,
147.1; MS (70 eV, EI) m/z = 319; HRMS (EI): m/z calcd for
C21H18ClN (M+): 319.1128, Found 319.1129.
1
Hz, 1H), 7.91 (d, J = 9.2 Hz, 1H), 7.85 (d, J = 8.4 Hz, 1H),
7.51–7.16 (m, 13H), 6.72–6.66 (m, 2H), 6.46 (dd, J = 6.0, 16.4
Hz, 1H), 5.24 (t, J = 4.8 Hz, 1H), 4.52 (d, J = 4.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ = 67.0, 104.6, 121.2, 121.5, 126.5,
127.2, 127.7, 127.8, 128.5, 128.9, 129.8, 129.9, 130.2, 131.4,
133.9, 136.4, 141.4, 143.2, 144.9, 146.3; IR (neat): 3409, 3270,
3058, 3026, 1622, 1595, 1514, 1464, 1380, 1238, 1122, 967,
909, 829, 734, 697 cm−1; MS (70 eV, EI) m/z = 336; HRMS
(EI): m/z calcd for C24H20N2 (M+): 336.1626, Found 336.1622.
(E)-N-(1,3-Diphenylallyl)-4-phenylquinolin-6-amine (3m):
1
light yellow oil; 85% yield; H NMR (400 MHz, CDCl3): δ =
8.69 (d, J = 4.8 Hz, 1H), 8.06 (d, J = 8.8 Hz, 1H), 7.42–7.17
(m, 18H), 6.85 (s, 1H), 6.55 (d, J = 16.0 Hz, 1H), 6.34 (dd, J =
6.4, 16.0 Hz, 1H), 5.00 (d, J = 6.4 Hz, 1H), 4.63 (s, 1H); 13C
NMR (100 MHz, CDCl3): δ = 67.0, 103.4, 121.4, 121.5, 126.5,
127.1, 127.6, 127.7, 127.9, 128.1, 128.4, 128.5, 128.8, 129.2,
130.0, 130.2, 131.7, 136.4, 138.4, 141.3, 143.1, 144.9, 145.5,
146.3; IR (neat): 3402, 3258, 3029, 1612, 1599, 1508, 1450,
1375, 1248, 1129, 968, 821, 738, 696 cm−1; MS (70 eV, EI) m/z
= 412; HRMS (EI): m/z calcd for C30H24N2 (M+): 412.1939,
Found 412.1941.
(E)-N-(1,3-Diphenylallyl)pyrimidin-2-amine (3n): light
yellow oil; 74% yield; 1H NMR (400 MHz, CDCl3): δ = 8.26 (d,
J = 4.0 Hz, 2H), 7.46–7.22 (m, 10H), 6.63 (d, J = 15.6 Hz, 1H),
6.54–6.42 (m, 2H), 6.09 (d, J = 8.0 Hz, 1H), 5.98–5.94 (m, 1H);
13C NMR (100 MHz, CDCl3): δ = 56.4, 110.9, 126.4, 127.1,
127.4, 127.5, 128.4, 128.6, 129.9, 130.6, 136.6, 141.6, 158.0,
161.5; IR (neat): 3412, 3251, 3021, 1599, 1495, 1465, 1368,
1250, 1122, 969, 817, 735, 697 cm−1; MS (70 eV, EI) m/z =
287; HRMS (EI): m/z calcd for C19H17N3 (M+): 287.1422,
Found 287.1421.
(E)-2-Chloro-N-(1,3-diphenylallyl)pyridin-4-amine
(3o):
1
light yellow oil; 89% yield; H NMR (400 MHz, CDCl3): δ =
7.92 (d, J = 6.0 Hz, 1H), 7.41–7.24 (m, 10H), 6.57 (d, J = 15.6
Hz, 1H), 6.48 (s, 1H), 6.40–6.29 (m, 2H), 5.13 (t, J = 5.6 Hz,
1H), 4.47 (d, J = 4.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
= 67.0, 107.1, 107.8, 126.5, 127.0, 128.0, 128.1, 128.3, 128.6,
129.1, 132.1, 135.9, 140.0, 149.3, 152.1, 154.2; IR (neat): 3417,
3247, 3016, 1601, 1587, 1501, 1447, 1382, 1237, 1121, 967,
820, 736, 696 cm−1; MS (70 eV, EI) m/z = 320; HRMS (EI): m/z
calcd for C20H17ClN2 (M+): 320.1080, Found 320.1081.
(E)-N-(1,3-bis(4-Dromophenyl)allyl)-4-nitroaniline
(3p):
1
light yellow oil; 81% yield; H NMR (400 MHz, CDCl3): δ =
8.04 (d, J = 9.2 Hz, 2H), 7.39–7.25 (m, 9H), 6.57–6.49 (m, 3H),
6.32 (dd, J = 6.4, 16.0 Hz, 1H), 5.18 (t, J = 6.0 Hz, 1H), 4.91
(d, J = 4.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ = 67.0,
112.1, 126.1, 127.7, 128.4, 128.7, 128.8, 129.3, 131.5, 133.9,
134.0, 134.2, 138.5, 138.7, 151.7; IR (neat): 3367, 2973, 1595,
N,N-bis((E)-1,3-Diphenylallyl)aniline (4a): light yellow oil;
52% yield; 1H NMR (400 MHz, CDCl3): δ = 7.45–7.20 (m,
22H), 7.01 (d, J = 7.2 Hz, 2H), 6.66–6.58 (m, 3H), 6.42–6.29
(m, 2H), 5.06 (d, J = 6.4 Hz, 1H), 4.77 (d, J = 7.6 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ = 53.3, 60.8, 113.6, 126.1, 126.2,
126.4, 127.0, 127.1, 127.4, 127.6, 128.3, 128.4, 128.5, 128.6,
128.7, 129.2, 130.7, 130.8, 131.0, 132.6, 133.2, 136.6, 137.4,
142.1, 144.0, 145.7; IR (neat): 3409, 3012, 2825, 1599, 1450,
1301, 1250, 1159, 969, 812, 745, 696 cm−1; MS (70 eV, EI) m/z
= 477; HRMS (EI): m/z calcd for C36H31N (M+): 477.2457,
Found 477.2453.
1493, 1303, 1182, 1107, 1010, 968, 906, 828, 729, 696 cm−1
;
MS (70 eV, EI) m/z = 486; HRMS (EI): m/z calcd for
C21H16Br2N2O2 (M+): 485.9579, Found 485.9581.
(E)-N-(3-(4-Dromophenyl)-1-phenylallyl)aniline (3q) and
(E)-N-(1-(4-bromo- phen-yl)-3-phenylallyl)aniline (3r): light
yellow oil; 75% yield; 1H NMR (400 MHz, CDCl3): δ =
7.47–7.12 (m, 13H), 6.77–6.73 (m, 1H), 6.68–6.59 (m, 3H),
6.40–6.35 (m, 1H), 5.12–5.08 (m, 1H), 4.12 (s, 1H); 13C NMR
(100 MHz, CDCl3): δ = 60.0, 60.5, 113.5, 113.6, 117.7, 117.9,
(E)-N-(1,3-Diphenylallyl)-N-methylaniline
(6a):
light
yellow oil; 81% yield; 1H NMR (400 MHz, CDCl3): δ =
7.44–7.25 (m, 13H), 6.88 (d, J = 8.4 Hz, 2H), 6.77 (t, J = 7.6
Hz, 1H), 6.57 (d, J = 4.8 Hz, 2H), 5.68 (d, J = 4.0 Hz, 1H), 2.84
This journal is © The Royal Society of Chemistry 2012
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(s, 3H); 13C NMR (100 MHz, CDCl3): δ = 33.8, 64.6, 113.2,
116.9, 126.5, 127.2, 127.4, 127.6, 127.8, 128.4, 128.5, 129.1,
132.7, 136.7, 140.6, 150.1; IR (neat): 3412, 3011, 2912, 1612,
7.45 (d, J = 7.6 Hz, 2H), 7.33–7.21 (m, 8H), 7.02 (d, J = 8.8
Hz, 2H), 6.94 (d, J = 8.4 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H), 6.66
(d, J = 8.0 Hz, 2H), 6.58 (d, J = 16.0 Hz, 1H), 6.43 (dd, J = 8.0,
16.0 Hz, 1H), 5.67 (d, J = 8.0 Hz, 1H), 3.78 (s, 3H), 2.23 (s,
3H); 13C NMR (100 MHz, CDCl3): δ = 20.3, 55.3, 67.1, 114.4,
118.1, 126.4, 126.9, 127.5, 128.1, 128.3, 128.4, 128.7, 129.3,
132.3, 136.9, 139.5, 141.6, 146.3, 156.3; IR (neat): 3027, 2920,
1479, 1441, 1313, 1249, 1150, 1122, 967, 812, 745, 697 cm−1
;
MS (70 eV, EI) m/z = 299; HRMS (EI): m/z calcd for C22H21N
(M+): 299.1674, Found, 299.1672.
(E)-N-(1,3-Diphenylallyl)-N-phenylaniline
(6b):
light
yellow oil; 87% yield; 1H NMR (400 MHz, CDCl3): δ = 7.44 (d,
J = 7.2 Hz, 2H), 7.31–7.16 (m, 14H), 6.94–6.88 (m, 4H), 6.58
(d, J = 15.6 Hz, 1H), 6.43 (dd, J = 8.4, 15.6 Hz, 1H), 5.74 (d, J
= 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ = 66.9, 117.7,
122.7, 122.9, 126.4, 127.0, 127.4, 127.5, 128.3, 128.4, 128.9,
129.2, 132.7, 141.2, 147.1; IR (neat): 3030, 2924, 1595, 1497,
1426, 1313, 1026, 969, 911, 748, 696 cm−1; MS (70 eV, EI) m/z
= 361; HRMS (EI): m/z calcd for C27H23N (M+): 361.1830,
Found 361.1831.
1613, 1507, 1447, 1242, 1180, 1033, 968, 809, 750, 698 cm−1
;
MS (70 eV, EI) m/z = 405; HRMS (EI): m/z calcd for C29H27NO
(M+): 405.2093, Found 405.2090.
(E)-N-(1,3-Diphenylallyl)-4-methoxy-N-(4-methoxyphenyl)
1
aniline (6h): light yellow oil; 69% yield; H NMR (400 MHz,
CDCl3): δ = 7.46 (d, J = 8.0 Hz, 2H), 7.33–7.21 (m, 8H), 6.86
(d, J = 8.8 Hz, 4H), 6.76 (d, J = 8.8 Hz, 4H), 6.57 (d, J = 15.6
Hz, 1H), 6.42 (dd, J = 7.6, 15.6 Hz, 1H), 5.62 (d, J = 8.0 Hz,
1H), 3.75 (s, 6H); 13C NMR (100 MHz, CDCl3): δ = 55.4, 67.0,
114.2, 124.1, 126.4, 126.9, 127.5, 127.6, 128.4, 128.5, 128.9,
132.2, 136.9, 141.4, 141.8, 154.5; IR (neat): 3026, 2950, 2833,
(E)-4-Chloro-N-(1,3-diphenylallyl)-N-phenylaniline (6c):
1
light yellow oil; 92% yield; H NMR (400 MHz, CDCl3): δ =
7.43–6.96 (m, 18H), 6.78 (d, J = 8.8 Hz, 2H), 6.58 (d, J = 15.6
Hz, 1H), 6.42 (dd, J = 7.6, 16.0 Hz, 1H), 5.71 (d, J = 7.2 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ = 67.0, 118.0, 118.7,
122.6, 122.9, 124.3, 125.9, 126.5, 127.2, 127.4, 127.7, 128.5,
128.8, 129.2, 133.0, 136.6, 140.8, 145.9, 146.7; IR (neat): 3029,
2928, 2360, 1591, 1491, 1450, 1309, 1252, 1093, 969, 816,
747, 697 cm−1; MS (70 eV, EI) m/z = 395; HRMS (EI): m/z
calcd for C27H22ClN (M+): 395.1441, Found 395.1444.
1604, 1504, 1454, 1239, 1178, 1036, 969, 822, 751, 698 cm−1
;
MS (70 eV, EI) m/z = 421; HRMS (EI): m/z calcd for
C29H27NO2 (M+): 421.2042, Found 421.2037.
(E)-N-(3-(4-Bromophenyl)-1-phenylallyl)-N-methylaniline
(6i) and (E)-N-(1-(4- bromophenyl)-3-phenylallyl)-N-methyl-
1
aniline (6j): light yellow oil; 65% yield; H NMR (400 MHz,
CDCl3): δ = 7.47–7.21 (m, 12H), 6.92–6.88 (m, 2H), 6.82–6.80
(m, 1H), 6.59–6.53 (m, 2H), 5.70–5.63 (m, 1H), 2.86–2.85 (m,
3H); 13C NMR (100 MHz, CDCl3): δ = 33.7, 33.8, 64.3, 64.6,
113.3, 113.4, 117.0, 117.3, 126.5, 126.9, 127.3, 127.7, 127.8,
127.9, 128.2, 128.3, 128.4, 128.5, 128.6, 128.7, 129.1, 129.2,
131.5, 133.0, 133.2, 135.2, 136.5, 139.2, 140.4, 149.9, 150.0;
IR (neat): 3417, 3026, 2927, 1605, 1499, 1447, 1412, 1397,
1313, 1250, 1095, 1015, 969, 912, 821, 749, 695 cm−1; MS (70
eV, EI) m/z = 377; HRMS (EI): m/z calcd for C22H20BrN (M+):
377.0779, Found 377.0776.
(E)-N-(1,3-Diphenylallyl)-4-methyl-N-phenylaniline (6d):
1
light yellow oil; 82% yield; H NMR (400 MHz, CDCl3): δ =
7.47–6.80 (m, 19H), 6.59 (d, J = 15.6 Hz, 1H), 6.45 (dd, J =
8.0, 16.0 Hz, 1H), 5.72 (d, J = 8.4 Hz, 1H), 2.29 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ = 20.7, 67.0, 118.5, 119.8, 119.9,
125.6, 126.4, 127.4, 127.5, 128.3, 128.4, 128.5, 128.7, 129.7,
130.0, 132.6, 136.8, 141.4, 144.0, 147.9; IR (neat): 3028, 2922,
1694, 1600, 1508, 1456, 1383, 1313, 1237, 1026, 970, 874,
814, 747, 698 cm−1; MS (70 eV, EI) m/z = 375; HRMS (EI): m/z
calcd for C28H25N (M+): 375.1987, Found 375.1984.
(E)-N-(1, 3-Diphenylallyl)benzamide (6k)13c: light yellow
solid; m.p. 150–152 °C; 90% yield; 1H NMR (400 MHz,
CDCl3): δ = 7.82 (d, J = 7.2 Hz, 2H), 7.52–7.21 (m, 13H), 6.43
(dd, J = 6.0, 16.0 Hz, 1H), 6.02 (t, J = 6.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ = 55.2, 126.5, 127.0, 127.2, 127.7, 127.8,
128.51, 128.54, 128.7, 128.8, 131.57, 131.69, 134.3, 136.3,
140.8, 166.4; MS (70 eV, EI) m/z = 313.
(E)-N-(1, 3-Diphenylallyl)acrylamide (6l): light yellow
solid; m.p.: 121–123 °C; 96% yield; 1H NMR (400 MHz,
CDCl3): δ = 7.37–7.22 (m, 10H), 6.56 (d, J = 16.4 Hz, 1H),
6.40–6.32 (m, 2H), 6.16 (dd, J = 6.2, 16.6 Hz, 1H), 6.07(bs,
1H), 5.90 (t, J = 7.0 Hz, 1H), 5.68 (d, J = 10.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ = 54.8, 126.5, 127.0, 127.1, 127.65,
127.7, 128.5, 128.6, 128.7, 130.6, 131.5, 136.3, 140.6, 164.6;
MS (70 eV, EI) m/z = 263; HRMS (EI): m/z calcd for C18H17NO
(M+): 263.1310, Found 263.1312.
(E)-1-N-(1, 3-Diphenylallyl)pyrrolidin-2-one (6m): light
yellow oil; 80% yield; 1H NMR (400 MHz, CDCl3): δ =
7.45–7.26 (m, 10H), 6.64 (d, J = 16.0 Hz, 1H), 6.47 (dd, J =
6.8, 16.0 Hz, 1H), 6.11 (d, J = 6.4 Hz, 1H), 3.47–3.41 (m, 1H),
3.17–3.11 (m, 1H), 2.56–2.42 (m, 2H), 2.12–1.94 (m, 2H); 13C
NMR (100 MHz, CDCl3): δ = 18.1, 31.1, 43.4, 56.2, 125.4,
126.5, 127.66, 127.7, 127.9, 128.60, 128.65, 133.4, 136.4,
138.7, 174.7; MS (70 eV, EI) m/z = 277; HRMS (EI): m/z calcd
for C19H19NO (M+): 277.1467, Found 277.1466.
(E)-N-(1,3-Diphenylallyl)-4-methoxy-N-phenylaniline (6e):
1
light yellow oil; 77% yield; H NMR (400 MHz, CDCl3): δ =
7.48 (d, J = 8.0 Hz, 1H), 7.36–7.24 (m, 10H), 7.17–7.10 (m,
4H), 6.88 (d, J = 8.8 Hz, 2H), 6.78–6.70 (m, 3H), 6.63 (d, J =
15.6 Hz, 1H), 6.45 (dd, J = 8.4, 16.0 Hz, 1H), 5.74 (d, J = 8.0
Hz, 1H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ = 55.3,
66.9, 114.5, 116.4, 117.9, 126.5, 127.0, 127.5, 128.4, 128.5,
128.6, 128.7, 130.3, 132.4, 136.8, 138.5, 141.4, 148.8, 157.1;
IR (neat): 3028, 1694, 1604, 1513, 1465, 1395, 1245, 1179,
1035, 836, 747, 698 cm−1; MS (70 eV, EI) m/z = 391; HRMS
(EI): m/z calcd for C28H25NO (M+): 391.1936, Found 391.1939.
(E)-N-(1,3-Diphenylallyl)-4-methyl-N-p-tolylaniline
(6f):
1
light yellow oil; 80% yield; H NMR (400 MHz, CDCl3): δ =
7.50–7.43 (m, 2H), 7.36–7.23 (m, 9H), 7.02 (d, J = 8.4 Hz, 4H),
6.86 (d, J = 8.4 Hz, 4H), 6.61 (d, J = 16.0 Hz, 1H), 6.49 (dd, J
= 7.6, 15.6 Hz, 1H), 2.27 (s, 6H); 13C NMR (100 MHz, CDCl3):
δ = 20.6, 67.1, 122.8, 124.2, 126.5, 126.9, 127.4, 127.5, 128.4,
128.5, 129.5, 130.9, 132.5, 136.9, 141.6, 145.0; IR (neat): 3026,
2919, 1610, 1510, 1450, 1227, 1109, 1028, 968, 807, 749,
697 cm−1; MS (70 eV, EI) m/z = 389; HRMS (EI): m/z calcd for
C29H27N (M+): 389.2143, Found 389.2144.
(E)-N-(1,3-Diphenylallyl)-4-methoxy-N-p-tolylaniline (6g):
1
light yellow oil; 72% yield; H NMR (400 MHz, CDCl3): δ =
4254 | Org. Biomol. Chem., 2012, 10, 4249–4255
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(E)-N-(1,
3-Diphenylallyl)-4-methylbenzenesulfonamide
(6n)13c: light yellow solid; m.p.: 133–135 °C; 97% yield; 1H
NMR (400 MHz, CDCl3): δ = 7.66–7.64 (m, 2H), 7.27–7.12 (m,
12H), 6.34 (d, J = 15.6 Hz, 1H), 6.07 (dd, J = 6.6, 15.8 Hz, 1H),
5.15–5.04 (m, 2H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ = 21.3, 59.6, 126.4, 126.9, 127.2, 127.7, 127.8, 128.0, 128.3,
128.6, 129.3, 132.0, 135.9, 137.6, 139.5, 143.1; MS (70 eV, EI)
m/z = 363.
14 T. Ohshima, Y. Miyamoto, J. Ipposhi, Y. Nakahara, M. Utsunomiya and
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Acknowledgements
This work was financially supported by the Natural Science
Foundation of China (no. 21072168 and no. 21102009), the Pri-
ority Academic Program Development of Jiangsu Higher Edu-
cation Institutions, and Natural Science Foundation of Jiangsu
Province (no. BK2011230).
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