Cooperative Palladium and Copper Catalysis: One-pot Synthesis of Diamino-Substituted Naphthalenes from Aryl Halides, 1,4-Bis(trimethylsilyl)butadiyne and Amines

Article abstract of DOI:10.1002/cctc.201901745

A one-pot method for the preparation of diamino-substituted naphthalene derivatives from easily available starting materials aryl halides, 1,4-bis(trimethylsilyl)butadiyne and amines is developed. Two C?N bonds, three C?C bonds and one aromatic ring are f

Full text of DOI:10.1002/cctc.201901745

Accepted Article
Title: Cooperative Palladium and Copper Catalysis: One-pot Synthesis
of Diamino-Substituted Naphthalenes from Aryl Halides, 1,4-
Bis(trimethylsilyl)butadiyne and Amines
Authors: Yuan Li, Shaozhong Qiu, Ling Fan, and Guodong Yin
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10.1002/cctc.201901745
ChemCatChem
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Cooperative Palladium and Copper Catalysis: One-pot Synthesis
of Diamino-Substituted Naphthalenes from Aryl Halides, 1,4-
Bis(trimethylsilyl)butadiyne and Amines
Yuan Li[a], Shaozhong Qiu[a], Ling Fan[a], and Guodong Yin*[a]
A
one-pot method for the preparation of diamino-substituted
route to diamino-substituted naphthalenes from aryl halides, 1,4-
bis(trimethylsilyl)butadiyne and amines (Scheme 1c).
naphthalene derivatives from easily available starting materials aryl
halides, 1,4-bis(trimethylsilyl)butadiyne and amines is developed.
Two C‒N bonds, three C‒C bonds and one aromatic ring are formed
in this domino process. This transformation is achieved by the
cooperative catalysis of Pd(OAc)2, Cu(Xantphos)I and Cu(OTf)2. A
possible
double
Sonogashira
coupling/hydroamination/
benzannulation reaction route is proposed.
Introduction
Scheme 1.Routes to functionalized diamino-substituted naphthalene
derivatives.
Polycyclic aromatic hydrocarbons (PAHs) are an important class
of organic conjugated molecules, which are widely used for
luminescent materials and molecular devices because of their
fascinating optical and electronic properties.[1] Development of a
new synthetic route to aromatic cores is crucial for obtaining
functionalized PAHs.[2] In recent years, much attention has been
paid to alkyne benzannulation as an effective approach to
construct aromatic cores.[3] 1,3-Diynes, as key building blocks in
organic synthesis,[4] can be attacked by nucleophiles to form a
variety of heterocycles,[5] including isoxazoles,[6] furans,[7]
pyrroles,[8] thiophenes,[9] pyridines,[10]pyrazoles,[11] pyrimidines,[12]
siloles,[13] and germoles.[14] However, few examples have been
reported for construction of a non-heteroaromatic ring system
using the four unsaturated carbon atoms of a 1,3-diyne.[15] Hua
was first to report the formation of diamino-substituted
naphthalene derivatives from diaryl 1,3-diynes and secondary
amines (Scheme 1a).[16] The reaction is limited to cyclic amines,
and excess amine is required because of its dual role of reactant
and solvent. Lee and co-workers found that diamino-substituted
naphthalenes could be prepared by the copper-catalyzed
reaction of aryl alkynyl carboxylic acids and amines (Scheme
1b).[17] These reported methods require the preparation of diaryl
1,3-diynes or aryl alkynyl carboxylic acids, respectively, as the
substrates. Accordingly, a new synthetic route to functionalized
diamino-substituted naphthalenes from easily available starting
materials is still desired. Recently, we found that 1,4-
bis(trimethylsilyl)butadiyne could be used as a linear linker to
1,4-diaryl-1,3-diynes catalyzed by the combination of Pd(OAc)2
and Cu(Xantphos)I.[18] In a continuation of our efforts to
construct PAHs,[19] herein we report a one-pot, five-component
Results and Discussion
Based on our previous results,[18a] when 4-bromobenzonitrile (1a)
was reacted with 1,4-bis(trimethylsilyl)buta-1,3-diyne (2) using
diethylamine (3a) as the base in the presence of Pd(OAc)2 and
Cu(Xantphos)I, an unexpected polycyclic aromatic hydrocarbon,
8-(4-cyanophenyl)-5,7-bis(diethylamino)-2-naphthonitrile
(4a),
was obtained in 27% yield (Table 1, entry 1). It can be seen that
the four unsaturated carbon atoms of 2 participated in the
formation of the benzene ring fragment. An electron-withdrawing
group (-CN) and electron-donating group (-NEt2) were
introduced into this conjugated molecule. Molecules bearing
these two classes of groups are widely used for fluorescent
materials.[20] A literature survey showed that copper salts can
facilitate both hydroamination and this cyclization process.[16,17,21]
After screening several commonly used copper salts including
CuCl, CuBr, CuI and Cu(OTf)2, a 59% NMR yield of 4a was
obtained when Cu(OTf)2 was used (entries 2–5). If the amount of
Cu(Xantphos)I and Cu(OTf)2 was increased, the yield reached
72% (entries 6–8). Increasing or decreasing the amount of 3a
was not conducive to this transformation (entries 9, 10).
With the optimized reaction conditions in hand (Table 1,
entry 8), the scope of aryl halides and amines was further
investigated (Table 2). Substrates bearing electron-withdrawing
groups (COMe, COOMe, COOEt, SO2Me, NO2, CF3) on the
para-position of the phenyl ring gave the corresponding diamino-
substituted naphthalenes 4b–4g in 40–63% yields. The structure
of 4e was confirmed by X-ray single crystal diffraction (Table 2,
CCDC 1949108). However, only a trace amount of product 4h
was observed when using 1-bromo-4-methoxybenzene as the
substrate, delivering the double Sonogashira coupling product
1,4-bis(4-methoxyphenyl)buta-1,3-diyne as the main product.
The possible reason is that the 1,3-diyne intermediate bearing
electron-donating group on the phenyl ring is unfavorable for the
nucleophilic addition of diethylamine to carbon-carbon triple
[a] Y. Li, S. Z. Qiu, L. Fan, Prof. G. D. Yin
College of Chemistry and Chemical Engineering, Hubei Key Laboratory of
Pollutant Analysis and Reuse Technology, Hubei Normal University,
Huangshi 435002, P. R. China.
E-mail: gdyin@hbnu.edu.cn
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/
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Table 2. The scope of aryl halides and amines[a]
bond.[21] 3-Bromobenzonitrile selectively gave 4i in 56% yield,
whose structure was also confirmed by X-ray single crystal
diffraction (Table 2, CCDC 1949109). 5-Bromo-1,2,3-
trifluorobenzene and 3-bromoquinoline were also suitable for
this reaction, giving 4j and 4k in moderate yields. When
dipropylamine (3b), dibutylamine (3c), piperidine (3d) and
morpholine (3e) were examined, 4l–4p were isolated in 36–58%
yields. Notably, for cyclic amines 3c and 3d, the corresponding
aryl iodides were used as the substrates in a two-step one-pot
procedure.
Table 1. Optimization of reaction conditions for the synthesis of 4a[a]
Pd(OAc)2
(mol%)
Cu(Xantphos)I
(mol%)
[Cu]
(mol%)
Yield[b]
(%)
Entry
1
2
3
4
5
6
1
1
1
1
1
1
1
1
1
1
1
1
none
27[c]
CuCl (5)
37
CuBr (5)
45
CuI (5)
53
Cu(OTf)2 (5)
Cu(OTf)2 (10)
59
66
7
1
1
Cu(OTf)2 (20)
69
8
9
1
1
1
5
5
5
Cu(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
72/60[c]
56[d]
10
49[e]
[a]
[a] The reactions were carried out using 1a (1.0 mmol), 2 (0.8 mmol) and 3a
(4.0 mmol) in DMF (4.0 mL) at 80 oC.
The reactions were carried out using 1 (1.0 mmol), 2 (0.8 mmol), 3 (4.0
mmol), Pd(OAc)2 (0.01 mmol), Cu(Xantphos)I (0.05 mmol) and Cu(OTf)2 (0.2
mmol) in DMF (4.0 mL) at 80 °C for 24 h; Isolated yield based on aryl halides.
[b] 8.0 mmol of 3a at 100 °C.
[b] NMR yield using 1,3,5-trimethoxybenzene as the internal standard.
[c] Isolated yield.
[c] Two-step reactions from aryl iodides in the presence of Cs2CO3.
[d] 6.0 mmol of 3a was used.
[e] 2.0 mmol of 3a was used.
During the synthesis of 4n, mono-amino substituted eneyne
4n′ was isolated in 15% yield. Subsequently, in an attempted
reaction of 4n′ with 3d in the presence of Cu(Xantphos)I, the
cyclization product 4n was obtained in 40% yield (Scheme 2a).
For this cyclization, Cu(OTf)2 was found to be a more effective
catalyst (Scheme 2b). The use of Pd(OAc)2 provided a similar
yield to Cu(OTf)2 for this cyclization (Scheme 2c). However, the
combination of Cu(Xantphos)I and Cu(OTf)2 effectively promoted
the formation of the product compared with the use of a single
catalyst (Scheme 2d).
(a) Cu(Xantphos)I (5% mmol), DMF (2.0 mL), 100 oC, N2, 24 h, 40%. (b)
Cu(OTf)2 (20% mmol), DMF (2.0 mL), 100 oC, N2, 24 h, 60%. (c) Pd(OAc)2 (1%
mmol), Cu(OTf)2 (20% mmol), DMF (2.0 mL), 100 oC, N2, 24 h, 61%. (d)
Cu(Xantphos)I (5% mmol), Cu(OTf)2 (20% mmol), DMF (2.0 mL), 100 oC, N2,
24 h, 82%.
Scheme 2. Controlled experiments.
On the basis of these results and previously reported work,
a preliminary reaction route was proposed using the synthesis of
4n as an example (Scheme 3). Initially, a double Sonogashira
coupling reaction of 1a with 2 gave the intermediate 4,4′-(buta-
1,3-diyne-1,4-diyl)dibenzonitrile (A) catalyzed by Pd(OAc)2 and
Cu(Xantphos)I.[18] Then an intermolecular hydroamination
reaction[16,17] occurred between A and 3d in the presence of
Cu(Xantphos)I and Cu(OTf)2, leading to the mono-amino
substituted eneyne 4n′ intermediate. The subsequent
hydroamination/benzannulation reaction furnished the target
product 4n.
Scheme 3. Proposed reaction route.
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Conclusions
47.6, 47.2, 12.6, 12.1; IR (KBr) ν: 757, 785, 838, 970, 1048, 1096, 1171,
1225, 1336, 1352, 1401, 1481, 1582, 1607, 1632, 1725, 2223, 2849,
2928, 2963 cm-1; HRMS m/z (ESI) calcd for C26H29N4: 397.2387, found:
397.2393 [M+H]+.
In summary, we have described a one-pot, five-component
reaction for the synthesis of diamino-substituted naphthalene
derivatives form aryl halides, 1,4-bis(trimethylsilyl)butadiyne and
amines. The four unsaturated carbon atoms of 1,4-
bis(trimethylsilyl)butadiyne participate in the formation of the
benzene ring fragment. Two C‒N bonds and three C‒C bonds
form in this domino process. The transformation is achieved
through cooperative catalysis of Pd(OAc)2, Cu(Xantphos)I and
1-(4-(7-Acetyl-2,4-bis(diethylamino)naphthalen-1-yl)phenyl)ethan-1-
one (4b)
Green solid; yield 40%, 86 mg; m.p. 116–118 °C; 1H NMR (300 MHz,
CDCl3) δ 8.33 (d, J = 8.8 Hz, 1H), 8.11–8.08 (m, 3H), 7.89 (dd, J1 = 8.8,
J2 = 1.7 Hz, 1H), 7.49 (d, J = 8.3 Hz, 2H), 7.20 (s, 1H), 3.25 (q, J = 7.1
Hz, 4H), 2.89 (q, J = 7.1 Hz, 4H), 2.71 (s, 3H), 2.47 (s, 3H), 1.10 (t, J =
7.1 Hz, 6H), 0.86 (t, J = 7.1 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 198.5,
198.1, 148.0, 147.1, 144.3, 135.5, 134.6, 133.6, 131.8, 130.3, 130.0,
128.2, 127.8, 124.8, 121.5, 116.7, 47.6, 47.4, 26.7, 26.6, 12.6, 12.2; IR
(KBr) ν: 837, 1163, 1223, 1267, 1355, 1601, 1675, 2970 cm-1; HRMS m/z
(ESI) calcd for C28H35N2O2:431.2693, found: 431.2694 [M+H]+.
Cu(OTf)2.
A
possible
double Sonogashira coupling/
hydroamination/benzannulation reaction route is proposed.
Electron-withdrawing groups and electron-donating amino
groups are simultaneously introduced into these functionalized
conjugated molecules. Both cyclic and acyclic secondary amines
are suitable for this kind of reaction. Compared with the reported
methods, although the reaction yield is relatively low and the
substrate is limited to aryl halides bearing electron-withdrawing
group on the aromatic ring, the advantage of easy operation and
easily available starting materials is still meaningful for this one-
pot multi-component reaction.
Methyl
5,7-bis(diethylamino)-8-(4-(methoxycarbonyl)phenyl)-2-
naphthoate (4c)
Yellow solid; yield 46%, 106 mg; m.p. 106–107 °C; 1H NMR (300 MHz,
CDCl3) δ 8.32 (d, J = 8.8 Hz, 1H), 8.20–8.15 (m, 3H), 7.92 (dd, J1 = 1.6
Hz, J2 = 8.8 Hz, 1H), 7.45 (d, J = 8.3 Hz, 2H), 7.19 (s, 1H), 3.97 (s, 3H),
3.85 (s, 3H), 3.24 (q, J = 7.1 Hz, 4H), 2.87 (q, J = 7.1 Hz, 4H), 1.10 (t, J =
7.0 Hz, 6H), 0.85 (t, J = 7.0 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 167.4,
167.3, 147.9, 147.0, 144.0, 133.6, 131.6, 130.2, 129.9, 129.4, 128.4,
128.3, 127.4, 124.5, 122.9, 116.4, 52.0, 47.6, 47.3, 12.6, 12.1; IR (KBr) ν:
762, 999, 1020, 1101, 1175, 1239, 1275, 1353, 1400, 1436, 1605, 1632,
1725, 2852, 2923, 2965 cm-1; HRMS m/z (ESI) calcd for C28H35N2O4:
463.2591, found: 463.2595 [M+H]+.
Experimental Section
GeneralInformation
The chemicals were commercially available without further purification.
1H NMR and 13C NMR (CDCl3 as the solvent) were recorded on Bruker
Avance II 300 MHz spectrometers at 300 MHzand 75 MHz respectively.
Chemical shifts are reported relative to tetramethylsilane (internal
standard). High resolution mass spectra were recorded on Solanx70 FT-
MS or Bruker ultrafleXtreme MALDI-TOF/TOF (HCCA matrix). Infrared
spectra were recorded on a Nicolet 5700 FTIR spectrometer using KBr
pellet samples. Column chromatography was performed on 200–300
mesh silica gel. Melting points were recorded on an uncorrected X-4
apparatus. The X-ray single crystal diffraction was recorded on a Bruker
Smart APEX CCD system.
Ethyl
5,7-bis(diethylamino)-8-(4-(ethoxycarbonyl)phenyl)-2-
naphthoate (4d)
Yellow liquid; yield 49%, 120 mg; 1H NMR (300 MHz, CDCl3) δ 8.31 (d, J
= 8.8 Hz, 1H), 8.22 (s, 1H), 8.16 (d, J = 7.1 Hz, 2H), 7.92 (d, J = 8.8 Hz,
1H), 7.45 (d, J = 7.1 Hz, 2H), 7.18 (s, 1H), 4.44 (q, J = 7.1 Hz, 2H), 4.32
(q, J = 7.1 Hz, 2H), 3.24 (q, J = 6.9 Hz, 4H), 2.88 (q, J = 6.9 Hz, 4H), 1.45
(t, J = 7.1 Hz, 3H), 1.33 (t, J = 7.1 Hz, 3H), 1.10 (t, J = 6.9 Hz, 6H), 0.86
(t, J = 7.1 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 167.0, 166.9, 147.9,
146.9, 143.9, 133.6, 131.6, 130.2, 130.0, 129.3, 128.6, 128.5, 127.8,
124.4, 122.9, 116.4, 60.9, 60.8, 47.6, 47.4, 14.4, 14.3, 12.6, 12.2; IR
(KBr) ν: 711, 778, 860, 1022, 1068, 1100, 1175, 1239, 1275, 1367, 1400,
1446, 1558, 1606, 1632, 1719, 2851, 2927, 2971 cm-1; HRMS m/z (ESI)
calcd for C30H39N2O4: 491.2904, found: 491.2910 [M+H]+.
General one-pot procedure for the synthesis of 4a–4m. A mixture of
aryl bromides 1 (1.0 mmol) and 1,4-bis(trimethylsilyl)butadiyne 2 (0.8
mmol) and amines 3 (4.0 mmol), Pd(OAc)2 (0.01 mmol, 2.3 mg),
Cu(Xantphos)I (0.05 mmol, 38.5 mg), Cu(OTf)2 (0.2 mmol, 72 mg) in
anhydrous DMF (4.0 mL) was stirred at 80 oC for 24 h under nitrogen
atmosphere. When the reactions were completed, the solvent DMF was
evaporated under reduced pressure. Then the mixture was extracted
three times with EA (3×15 mL), and the combined organic layers were
dried over anhydrous magnesium sulfate and filtered. After evaporation
of the solvent, the residue was purified by column chromatography on
silica gel using PE or the mixture of EA/PE (1:100 to 1:1) as the eluent to
deliver the target products.
N1,N1,N3,N3-Tetraethyl-6-(methylsulfonyl)-4-(4-(methylsulfonyl)-
phenyl)naphthalene-1,3-diamine (4e)
Yellow solid; yield 62%, 156 mg; m.p. 191–193 °C; 1H NMR (300 MHz,
CDCl3) δ 8.48 (d, J = 8.9 Hz, 1H), 8.11 (d, J = 1.7 Hz, 1H), 8.09 (s, 1H),
8.06 (s, 1H), 7.78 (dd, J1 = 1.8 Hz, J2 = 8.9 Hz, 1H), 7.59 (d, J = 8.4 Hz,
2H), 7.24 (s, 1H), 3.26 (q, J = 7.1 Hz, 4H), 3.21 (s, 3H), 3.03 (s, 3H), 2.86
(q, J = 7.1 Hz, 4H), 1.11 (t, J = 7.1 Hz, 6H), 0.85 (t, J = 7.1 Hz, 6H); 13
C
NMR (75 MHz, CDCl3) δ 148.6, 148.5, 144.3, 139.0, 137.8, 133.2, 132.4,
130.0, 128.3, 127.5, 126.4, 125.6, 119.8, 117.3, 47.7, 47.0, 44.6, 44.4,
12.4, 12.1; IR (KBr) ν: 768, 954, 1089, 1125, 1152, 1226, 1314, 1401,
1581, 1593, 1631, 2811, 2929, 2973, 3203 cm-1; HRMS m/z (ESI) calcd
for C26H35N2O4S2: 503.2033, found: 503.2036 [M+H]+.
8-(4-Cyanophenyl)-5,7-bis(diethylamino)-2-naphthonitrile (4a)
Yellow solid; yield 60%, 119 mg; m.p. 138–139 °C; 1H NMR (300 MHz,
CDCl3) δ 8.35 (d, J = 8.2 Hz, 1H), 7.80 (d, J = 8.2 Hz, 2H), 7.74 (d, J =
1.2 Hz, 1H), 7.49–7.44 (m, 3H), 7.20 (s, 1H), 3.24 (q, J = 7.1 Hz, 4H),
2.88 (q, J = 7.1 Hz, 4H), 1.10 (t, J = 7.1 Hz, 6H), 0.85 (t, J = 7.1 Hz, 6H);
13C NMR (75 MHz, CDCl3) δ 148.6, 148.1, 143.4, 133.3, 132.2 (2C),
131.1, 129.3, 127.5, 125.7, 124.1, 119.6, 119.0, 117.0, 110.8, 109.7,
N1,N1,N3,N3-Tetraethyl-6-nitro-4-(4-nitrophenyl)naphthalene-1,3-
diamine (4f)
Red solid; yield 63%, 137 mg; m.p. 116–117 °C; 1H NMR (300 MHz,
CDCl3) δ 8.42–8.38 (m, 3H), 8.34 (d, J = 2.1 Hz, 1H), 8.11–8.07 (m, 1H),
7.57 (d, J = 8.8 Hz, 2H), 7.24 (s, 1H), 3.27 (q, J = 7.1 Hz, 4H), 2.90 (q, J
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= 7.1 Hz, 4H), 1.12 (t, J = 7.1 Hz, 6H), 0.88 (t, J = 7.1 Hz, 6H); 13C NMR
(75 MHz, CDCl3) δ 148.9, 148.6, 146.9, 146.1, 145.4, 133.1, 132.4, 130.4,
128.3, 126.3, 123.7, 121.4, 117.6, 116.9, 47.6, 47.1, 12.5, 12.1; IR (KBr)
ν: 706, 861, 1063, 1165, 1237, 1342, 1401, 1532, 1631, 2925, 2966 cm-1;
HRMS m/z (ESI) calcd for C24H29N4O4: 437.2183, found: 437.2189
[M+H]+.
Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 149.2, 148.8, 143.6, 133.4, 132.3,
132.2, 130.9, 128.8, 126.2, 125.6, 123.9, 119.6, 118.9, 116.6, 110.8,
109.6, 55.9, 55.2, 20.7, 20.1, 11.7, 11.5; IR (KBr) ν: 756, 831, 943, 1068,
1125, 1219, 1299, 1400, 1589, 1631, 2227, 2873, 2965, 3208 cm-1;
HRMS m/z (ESI) calcd for C30H37N4: 453.3013, found: 453.3017 [M+H]+.
8-(4-Cyanophenyl)-5,7-bis(dibutylamino)-2-naphthonitrile (4m)
Yellow liquid; yield 55%, 140 mg; 1H NMR (300 MHz, CDCl3) δ 8.32 (d, J
= 8.7 Hz, 1H), 7.81 (d, J = 8.2 Hz, 2H), 7.73 (d, J = 1.2 Hz, 1H), 7.46 (d, J
= 8.2 Hz, 3H), 7.22 (s, 1H), 3.16 (t, J = 7.5 Hz, 4H), 2.81 (t, J = 7.7 Hz,
4H), 1.56–1.46 (m, 4H), 1.34–1.08 (m, 12H), 0.91–0.85 (m, 6H), 0.80 (t, J
= 7.2 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 149.1, 148.7, 143.6, 133.3,
132.2 (2C), 130.9, 128.7, 126.1, 125.5, 123.8, 119.5, 118.9, 116.6, 110.7,
109.6, 53.8, 53.0, 29.6, 29.1, 20.4, 20.2, 13.9, 13.8; IR (KBr) ν: 557, 756,
831, 1124, 1212, 1262, 1400, 1587, 1631, 2227, 2860, 2929, 2959 cm-1;
HRMS m/z (ESI) calcd for C34H45N4: 509.3639, found: 509.3641 [M+H]+.
N1,N1,N3,N3-Tetraethyl-6-(trifluoromethyl)-4-(4-(trifluoromethyl)-
phenyl)naphthalene-1,3-diamine (4g)
Yellow solid; yield 41%, 99 mg; m.p. 94–96 °C; 1H NMR (300 MHz,
CDCl3) δ 8.41 (d, J = 8.8 Hz, 1H), 7.76–7.72 (m, 3H), 7.53–7.46 (m, 3H),
7.20 (s, 1H), 3.25 (q, J = 7.1 Hz, 4H), 2.88 (q, J = 7.1 Hz, 4H), 1.10 (t, J =
7.0 Hz, 6H), 0.85 (t, J = 7.1 Hz, 6H);13C NMR (75 MHz, CDCl3) δ 148.2,
147.7, 142.5, 133.4, 131.8, 129.2 (q, JC-F = 38.7 Hz), 127.9 (q, JC-F = 31.2
Hz), 125.6, 125.1 (d, JC-F = 3.6 Hz), 124.5 (q, JC-F = 270.4 Hz), 122.9,
122.8, 119.1 (d, JC-F = 3.1 Hz), 116.2, 47.7, 47.4, 12.6, 12.2; IR (KBr) ν:
588, 700, 735, 834, 962, 1020, 1067, 1119, 1158, 1261, 1311, 1325,
1370, 1588, 1616, 1631, 1801, 1922, 2847, 2933, 2974 cm-1; HRMS m/z
(ESI) calcd for C26H29F6N2: 483.2229, found: 483.2225 [M+H]+.
5-(3-Cyanophenyl)-6,8-bis(diethylamino)-2-naphthonitrile (4i)
Yellow solid; yield 56%, 111 mg; m.p. 135–136 °C; 1H NMR (300 MHz,
CDCl3) δ 8.66 (s, 1H), 7.72–7.65 (m, 2H), 7.61–7.59 (m, 2H), 7.41 (s, 2H),
7.13 (s, 1H), 3.25 (q, J = 7.1 Hz, 4H), 2.90 (q, J = 7.1 Hz, 4H), 1.11 (t, J =
7.1 Hz, 6H), 0.86 (t, J = 7.1 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 149.9,
149.1, 139.8, 136.1, 135.8, 135.1, 130.9, 130.4, 129.2, 126.8, 126.7,
125.9, 125.7, 120.0, 118.9, 115.4, 112.5, 106.4, 47.7, 46.9, 12.5, 12.1; IR
(KBr) ν: 788, 810, 920, 1068, 1084, 1199, 1218, 1235, 1333, 1374, 1402,
1452, 1573, 1609, 1631, 2221, 2827, 2931, 2970, 3213 cm-1; HRMS m/z
(ESI) calcd for C26H29N4: 397.2387, found: 397.2381 [M+H]+.
General one-pot procedure for the synthesis of 4n–4p. A mixture of
aryl iodides 1 (1.0 mmol), 1,4-bis(trimethylsilyl)butadiyne 2 (0.5 mmol),
Pd(OAc)2 (0.01 mmol, 2.3 mg), Cu(Xantphos)I (0.05 mmol, 38.5 mg) and
Cs2CO3 (2.0 mmol, 652 mg) in anhydrous DMF (4.0 mL) was stirred at
room temperature for 16 h under nitrogen atmosphere. Then amines 3
(10.0 mmol) and Cu(OTf)2 (0.2 mmol, 72 mg) were added and the
o
temperature was increased to 100 C for 24 h. When the reactions were
completed, the solvent DMF was evaporated under reduced pressure.
Then the mixture was extracted three times with EA (3×15 mL), and the
combined organic layers were dried over anhydrous magnesium sulfate
and filtered. After evaporation of the solvent, the residue was purified by
column chromatography on silica gel using PE or the mixture of EA/PE
(1:100 to 1:1) as the eluent to deliver the target products.
N1,N1,N3,N3-Tetraethyl-5,6,7-trifluoro-4-(3,4,5-trifluorophenyl)-
naphthalene-1,3-diamine (4j)
8-(4-Cyanophenyl)-5,7-di(piperidin-1-yl)-2-naphthonitrile (4n)
Yellow solid; yield 39%, 89 mg; m.p. 68–70 °C; 1H NMR (300 MHz,
CDCl3) δ 7.96–7.89 (m, 1H), 7.12 (s, 1H), 6.94–6.86 (m, 2H), 3.16 (q, J =
7.1 Hz, 4H), 2.84 (q, J = 7.1 Hz, 4H), 1.06 (t, J = 7.1 Hz, 6H), 0.85 (t, J =
7.1 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 152.2, 150.4, 148.9, 148.3,
145.1, 140.9, 140.2, 136.9, 136.0, 129.9, 126.6, 125.0, 121.8, 116.1,
114.7, 114.4, 105.5, 105.2, 47.8, 47.7, 12.7, 12.1; IR (KBr) ν: 766, 869,
1037, 1115, 1221, 1236, 1379, 1471, 1534, 1613, 1631, 2849, 2918,
2973 cm-1; HRMS m/z (ESI) calcd for C24H25F6N2: 455.1916, found:
455.1920 [M+H]+.
Yellow solid; yield 36%, 76 mg; m.p. 270–272 °C; 1H NMR (300 MHz,
CDCl3) δ 8.21 (d, J = 8.7 Hz, 1H), 7.82–7.79 (m, 3H), 7.52–7.44 (m, 3H),
7.09 (s, 1H), 3.08 (s, 3H), 2.81 (t, J = 5.4 Hz, 4H), 1.86 (q, J = 5.4 Hz,
4H), 1.42–1.29 (m, 9H); 13C NMR (75 MHz, CDCl3) δ 152.5, 151.1, 143.2,
132.8, 132.4, 132.2, 131.0, 126.9, 125.4, 124.5, 123.8, 119.6, 119.0,
111.9, 110.7, 109.8, 54.6, 53.0, 26.5, 26.0, 24.4, 24.0; IR (KBr) ν: 829,
857, 1036, 1093, 1112, 1224, 1261, 1361, 1381, 1439, 1503, 1586, 1601,
1655, 2225, 2854, 2929 cm-1; HRMS m/z (ESI) calcd for C28H29N4:
421.2387, found: 421.2396 [M+H]+.
N7,N7,N9,N9-Tetraethyl-10-(quinolin-3-yl)phenanthridine-7,9-diamine
(E)-4,4'-(1-(Piperidin-1-yl)but-1-en-3-yne-1,4-diyl)dibenzonitrile (4n’)
Gray solid; yield 15%, 25 mg; m.p. 158–160 °C; 1H NMR (300 MHz,
CDCl3) δ 7.66–7.51 (m, 4H), 7.47–7.41 (m, 2H), 7.32 (d, J = 8.4 Hz, 2H),
6.14 (s, 1H), 3.99 (t, J = 5.5 Hz, 2H), 3.81 (s, 2H), 2.72 (t, J = 6.2 Hz, 2H),
1.92–1.86 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 147.4, 137.6, 132.2,
130.5, 129.5, 129.3, 127.8, 119.2, 117.0, 111.0, 109.6, 109.0, 45.4, 32.3,
23.8, 22.3, 20.4; IR (KBr) ν: 805, 1144, 1384, 1513, 1601, 2218 cm-1;
HRMS m/z (ESI) calcd for C23H21N3: 338.1651, found: 338.1645 [M+H]+.
1,1'-(6-Nitro-4-(4-nitrophenyl)naphthalene-1,3-diyl)dipiperidine (4o)
Yellow solid; yield 39%, 90 mg; m.p. 267–269 °C; 1H NMR (300 MHz,
CDCl3) δ 8.41 (d, J = 2.0 Hz, 2H), 8.38 (s, 1H), 8.27 (d, J = 9.2 Hz, 1H),
8.06 (dd, J1 = 2.2 Hz, J2 = 9.2 Hz, 1H), 7.61 (d, J = 8.6 Hz, 2H), 7.14 (s,
1H), 3.11 (s, 4H), 2.84 (t, J = 5.3 Hz, 4H), 1.91–1.85 (m, 4H), 1.71 (s, 2H),
1.42–1.35 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 152.7, 151.7, 146.8,
146.2, 145.3, 132.8, 132.5, 128.1, 126.0, 125.4, 123.7, 121.4, 116.6,
112.5, 54.6, 53.0, 26.5, 26.0, 24.4, 24.0; IR (KBr) ν: 809, 857, 1011, 1103,
1213, 1341, 1386, 1440, 1518, 1587, 1631, 2813, 2851, 2937 cm-1;
(4k)
Yellow solid; yield 45%, 101 mg; m.p. 144–146 °C; 1H NMR (300 MHz,
CDCl3) δ 9.72 (s, 1H), 9.00 (d, J = 2.1 Hz, 1H), 8.22 (d, J = 8.9 Hz, 1H),
8.08–8.03 (m, 2H), 7.80–7.75 (m, 2H), 7.59–7.57 (m, 1H), 7.54–7.43 (m,
1H), 7.29–7.26 (m, 2H), 6.93–6.87 (m, 1H), 3.36 (q, J = 7.1 Hz, 4H),
2.82–2.79 (m, 4H), 1.18 (t, J = 7.1 Hz, 6H), 0.82 (t, J = 7.1 Hz, 6H); 13C
NMR (75 MHz, CDCl3) δ 153.7, 153.6, 150.7, 150.4, 146.6, 146.2, 137.2,
134.3, 134.0, 129.5, 129.2 (2C), 128.2, 127.8, 127.7, 127.3, 126.5, 126.3,
124.9, 124.2, 120.8, 115.7, 48.3, 47.1, 12.3, 12.2; IR (KBr) ν: 768, 1047,
1108, 1172, 1222, 1353, 1401, 1579, 1631, 2813, 2926, 2967, 3177 cm-
1; HRMS m/z (ESI) calcd for C30H33N4: 449.2700, found: 449.2701
[M+H]+.
8-(4-Cyanophenyl)-5,7-bis(dipropylamino)-2-naphthonitrile (4l)
Yellow liquid; yield 58%, 131 mg; 1H NMR (300 MHz, CDCl3) δ 8.34 (d, J
= 8.7 Hz, 1H), 7.81 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 1.1 Hz, 1H), 7.48–
7.45 (m, 3H), 7.23 (s, 1H), 3.16–3.11 (m, 4H), 2.80–2.75 (m, 4H), 1.62–
1.49 (m, 4H), 1.35–1.22 (m, 4H), 0.89 (t, J = 7.4 Hz, 6H), 0.71 (t, J = 7.4
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10.1002/cctc.201901745
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HRMS m/z (ESI) calcd for C26H29N4O4: 461.2183, found: 461.2190
[M+H]+.
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4,4'-(6-Nitro-4-(4-nitrophenyl)naphthalene-1,3-diyl)dimorpholine (4p)
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CDCl3) δ 8.44 (s, 1H), 8.42 (d, J = 1.8 Hz, 2H), 8.34 (d, J = 9.2 Hz, 1H),
8.13 (dd, J1 = 2.2 Hz, J2 = 9.2 Hz, 1H), 7.64 (d, J = 8.7 Hz, 2H), 7.19 (s,
1H), 4.04 (t, J = 4.3 Hz, 4H), 3.52 (t, J = 4.3 Hz, 4H), 3.19 (t, J = 4.3 Hz,
4H), 2.91 (t, J = 4.4 Hz, 4H); 13C NMR (75 MHz, CDCl3) δ 151.4, 149.9,
147.1, 146.4, 144.3, 132.9, 132.3, 128.0, 126.5, 125.7, 123.9, 121.6,
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1069, 1112, 1226, 1262, 1308, 1345, 1443, 1522, 1582, 1631, 2847,
2917, 2962 cm-1; HRMS m/z (ESI) calcd for C24H25N4O6: 465.1769,
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Acknowledgements
We gratefully acknowledge support from the Educational
Commission of Hubei Province (D20192503) and the National
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FULL PAPER
Yuan Li, Shaozhong Qiu, Ling Fan, Prof.
Guodong Yin*
1–5
Cooperative Palladium and Copper
Catalysis: One-pot Synthesis of
Cooperative catalysis: The diamino-substituted naphthalene derivatives are
synthesized from easily available starting materials aryl halides, 1,4-
bis(trimethylsilyl)butadiyne and amines in a one-pot procedure by the cooperative
action of Pd(OAc)2, Cu(Xantphos)I and Cu(OTf)2.
Diamino-Substituted
Naphthalenes
from Aryl Halides,
Bis(trimethylsilyl)butadiyne
Amines
1,4-
and
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