Br?nsted acid/visible-light-promoted Markovnikov hydroamination of vinylarenes with arylamines

Article abstract of DOI:10.1039/c9ob02457c

A Br?nsted acid/visible-light-promoted Markovnikov hydroamination of vinylarenes with arylamines in the presence of TPT and CF₃CO₂H has been developed. This transformation provides a green approach to alpha-amino-substituted arylalkanes under metal-free conditions.

Full text of DOI:10.1039/c9ob02457c

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DOI: 10.1039/C9OB02457C
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PAPER
Bronsted Acid/Visible-Light-Promoted Markovnikov
Hydroamination of Vinylarenes with Arylamines†
Received 00th January 201x,
Accepted 00th January 201x
Jiao Gui,a Haisheng Xie,a Fengjuan Chen,a Zhipeng Liu,a Xiaoqi Zhang,b Fubin
Jiang,c and Wei Zeng a,*
DOI: 10.1039/x0xx00000x
A Bronsted acid/visible-light-promoted Markovnikov hydroamination of vinylarenes with arylamines in the presence of TPT
and CF3CO2H has been developed. This transformation provides a green approach to alpha-amino-substituted arylalkanes
under metal-free conditions.
www.rsc.org/
oxidized alkylamines to its‘ aminium radical cations (ARCs), the
followed N-centered radical addition to alkenes led to the
Introduction
formation of anti-Markovnikov products
Meanwhile, many works have proved that photocatalytical
system could also activate alkenes to form triplet alkenes (
through energy-transfer (EnT).9 We were therefore aware that
(
Scheme 1b).8

-Arylalkylamines are often encountered in natural products,
pharmaceuticals and bioactive small molecules, and also
served as useful synthons to construct complex nitrogen-
T
)
containing organic molecules.1 In the past decades, great the photoexcited alkenes could also trap a proton to produce
alkyl carbocations (CCs) in the presence of Bronsted acids,
which could subsequently react with amines to afford the
corresponding Markovnikov products (Scheme 1c).
progress has been made to assemble these high value amines
through cross-coupling reaction,2 nucleophilic addition3 and C-
H
bond nitrene insertion.4 In comparison, the direct
hydroamination of alkenes with amines provides a 100% atom-
efficient method without the formation of byproducts.
However, this methodology suffers from high activation
barriers and regioselectivity issues.5 In these regards, earth-
rich transition-metal Fe, Co, Ni, Zn, or V-catalyzed
hydroamination of olefins could synchronously produce
Markovnikov and anti-Markovnikov products under high
reaction temperature
(
Scheme 1a).6 In contrast,
regioselectively assembling hydroamination products demands
noble metal Rh, Pd or Ir-catalytical system.7 Thus, there
remains
a
need for exploring
a
new regioselective
hydroamination strategy of alkenes to avoid usage of
expensive metal catalysts and harsh conditions.
Recently, visible-light-induced photo catalysis provides a
green platform for chemical transformation at ambient
temperature, thus also possibly enabling the hydroamination
of alkenes by replacing the conventional catalytical approaches.
As
a
consequence, Knowles achieved
in photo-promoted
a
significant
breakthrough
intermolecular
hydroamination of unactive alkenes with secondary
alkylamines, in which the excited-state redox Ir-catalysts first
Scheme 1. Hydroamination strategies of alkenes
Results and discussion
aChina Key Laboratory of Functional Molecular Engineering of Guangdong Province,
School of Chemistry and Chemical Engineering, South China University of
Technology, Guangzhou 510641, China
To verify this feasibility, we commenced our investigation by
studying the intermolecular hydroamination of 4-
methoxystyrene (1a) and 4-chloroaniline (2a), and found the
mixture of 1a (0.1 mmol), 2a (0.2 mmol), 2,4,6-
triphenylpyrylium tetrafluoroborate (TPT, 5 mol %), and
bGuangdong Provincial Engineering Research Center for Modernization of TCM,
College of Pharmacy, Jinan University, Guangzhou 510632, China
cCollege of Chemistry, Beijing Normal University, Beijing 100875, China
†
Electronic supplementary information (ESI) available: 1H and 13C NMR spectra,
mass of the compounds see DOI: 10.1039/x0xx00000x
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CF3CO2H (0.1 mmol) in trifluoroethanol (TFE 1.0 mL) was
Journal Name
With an optimized protocol in hand, we then examined the
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DOI: 10.1039/C9OB02457C
irradiated with green LEDs (520 nm, 30 W) for 10 h under an substrate scope with respect to the arylamine component
air
atmosphere
at
room
temperature.

-(N-(4-
(Scheme 2). In general, different kinds of halo-substituted
chlorophenyl)amino)-

-(4-meth oxyphenyl)ethane (3-1a) was arylamines
including 4-chlorophenylamine, 4-
obtained in 81% yield after chromatogaphic isolation (Table 1, fluorophenylamine, 4-bromophenylamine, 4-iodophenylamine,
entry 1). In comparison, other organo- or noble-metal photo- and even electron-deficient 4-chloro-3-(trifluoromethyl)aniline
catalysts such as Eosin Y, [Mes-Acr]ClO4, Hantzsch ester (HEH), and 4-chloro-3-nitroaniline could smoothly react with 4-
Ru(bpy)3Cl2 and [Ir(dtbbpy)(ppy)2][PF6] gave us considerably methoxystyrene 1a to regioselectively produce the
lower yields (entries 2-6, 36-57%). Evaluation of different corresponding Markovnikov -phenylethylamines 3-1a-3-1g in
Bronsted acids indicated that the hydroamination reaction of good to excellent yields (61-81%). Meanwhile, electron-rich
1a and 2a in the presence of TfOH, TsOH and 2,3,4,5- arylamines such as para- or meta-alkyl- and para- methoxy-
tetrafluoro benzoic acids (TFBA) could occur with lower yields substituted anilines could also be efficiently converted into the
(58-76%) (entries 7-9), and no desired product 3-1a could be target hydroamination products 3-1i, 3-1j, 3-1l-3-1p in 61-75%
observed in the absence of Bronsted acids (entry 10). yields. However, 2-methylaniline only gave us 29% yield of 3-
Meanwhile, employing 0.2 and 0.5 equ. of CF3CO2H led to 16% 1k due to steric hindrance. Gratifyingly, 4-phenylaniline,
and 47% yield of 3-1a (entry 1 vs 11 and 12), respectively, heteroarylamines (8-aminoquinoline and indoline) could still
indicating that CF3CO2H plays an indispensable role of undergo highly regioselective hydroamination with alkene 1a
bronsted acid-catalyst; using blue LEDs as light source led to 50% to furnish moderate yields of 3-1q-3-1s (41-58%). Notably,
yield of 3-1a (entry 13 vs 1). It should be noted that the when 1-aminonaphthalene and N-ethylaniline were subjected
transformation still afforded 57% and 49% yield of 3-1a to this photocatalytic system, an unexpected reductive
without the photoirradiation and photocatalysts, respectively coupling between aryl Csp2-H bonds and alkenes occurred at
(entries 14 and 15). These combined facts (entries 1, and 10-15) the para-positin of amino group possibly due to the electron-
demonstrated that CF3CO2H solely promoted the rich property and steric hindrance of arylamines, providing the
intermolecular hydroamination of 1a with 2a to a certain corresponding arylalkylation products 3-1t (72%) and 3-1u
degree, and the green light possibly induced TPT catalyst to (55%), respectively.
further activate the alkene 1a
, resulting in increased
conversions.
Scheme 2. Arylamine scope a, b
Table 1. Optimization of the reaction parameters a
entry
Changes to standard conditions Yield of 3-1a (%) b
1
2
3
4
5
6
7
8
9
none
EosinY
[Mes-Acr]ClO4
HEH
81
57
40
51
41
36
58
76
62
0
Ru(bpy)3Cl2
[Ir(dtbbpy)(ppy)2][PF6]
TfOH
TsOH
TFBA
no acids
10
11
CF3CO2H (0.2 equ.)
16
12
CF3CO2H (0.5 equ.)
47
13
14
15
30 W blue LEDs
no light
50
57
49
No PC
a
Reaction conditions: 0.1 mmol of 4-methoxystyrene
1a, 0.2 mmol of 4-chloroaniline 2a, photo catalyst TPT
( 5 mol %), and CF3CO2H (1.0 equiv) in TFE (1.0 mL)
under an air atmosphere at room temperature for 10 h,
a
green LED light. b Isolated yield
.
Reaction conditions: 0.1 mmol of 4-
methoxystyrene 1a, 0.2 mmol of arylamines 2, TPT
( 5 mol %), and CF3CO2H (1.0 equiv) in TFE (1.0
mL) under an air atmosphere at room temperature
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b
c
for 10 h, green LED light. Isolated yield. Isolated
yield in the absence of TPT.
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DOI: 10.1039/C9OB02457C
We next evaluated this transformation of 4-chloroaniline 2a
with various alkenes (Scheme 3), and found electron-rich
alkenes such as 3,4-dimethoxystyrene and 4-(tert-
butyl)styrene could furnish the respective hydroamination
products 3-2a (73%) and 3-2b (77%), respectively. Interestedly,
the reaction between 4-methylstyrene and 4-chloroaniline 2a
gave a coupling-cyclization product 1, 2, 3, 4-tetrahydro
a
Reaction conditions: 0.1 mmol of aryl unsaturated
carbons 1, 0.2 mmol of 4-chloroaniline 2a, TPT ( 5
mol %), and CF3CO2H (1.0 equiv) in TFE (1.0 mL)
under an air atmosphere at room temperature for 10 h,
green LED light. Isolated yield. c 80 C for 24 h.
b
o
d
Isolated yield in the absence of TPT.
quinoline 3-2c (30%) instead of N-branched -arylalkylamine,
possibly due to that the solvent CF3CH2OH was oxidized into
aldehydes, followed by the detrifluoromethylation and
condensation with 2a and cyclozation with 4-methylstyrene.10
4-Hydroxylstyrene only gave 40% yield of 3-2d at room
To ascertain mechanistic insights, we first performed the
photocatalyzed hydroamination of 4-methoxystyrene 1a with
4-chloroaniline 2a in the presence of TEMPO (3.0 equiv), and
78% yield of 3-1a was obtained, indicating that a single-
temperature. On the contrary, 3-fluoro-4-methoxystyrene, 3- electron transfer (SET) photoredox process was not possibly
involved in the transformation (Scheme 4a). Subsequently, the
photocatalyzed hydroamination of styrene 1a with arylamine
2a did not occur in the absence of CF3CO2H (Scheme 4b), but
employing PhI(OAc)2 could still furnish 34% yield of 3-1a
chloro-4-methoxystyrene, 3-bromo-4-methoxystyrene and 3-
trifluoromethyl-4-methoxystyrene underwent moderate
conversions only under heating conditions (80 oC), affording
41-68% yields of -arylalkyl amines 3-2e To our
3-2h 11
delight, when internal alkenes such as 1-(4-methoxyphenyl)-1-
propene and 6-methoxy-1H-indene were employed as

~
.
(Scheme 4c), these two control experiments implied that
Bronsted acids or Lewis acids could interact with arylamines to
form activated aminium ion intermediates.12 Moreover,
employing strong electron-donating methylenedioxy group
substituted aniline (2v) as a substrate to react with 4-
methoxystyrene 1a synchronously gave hydroamination
product 3-1v (28%) and arylalkylation product 3-1w (52%)
substrates to react with arylamine 2a, -aryl alkylamines 3-2i
(45%) and 3-2j (25%) could be still obtained through high-regio
selective hydroamination. Unfortunately, when electron-neutral
and electron-deficient vinylarenes such as styrene, 1-
(trifluoromethyl)-4-vinylbenzene, and 1-chloro-4-vinylbenzene were
subjected to the standard reaction conditions, no desired -
arylalkylamines 3-2k, 3-2l, and 3-2m were observed, Finally, we
tried the hydroamination of electron-rich terminal and internal
(Scheme 4d), indicating benzyl carboncations were also
possibly involved in this transformation.
On the other hand, Stern-Volmer fluorescence quenching
analysis suggested that photoexcited TPT* was quenched
alkynes 4a and 4b with arylamine 2a under TPT-photocatalytic mainly by styrene 1a. On the contrary, the representative
amine 2a and CF3CO2H did not decrease the phosphorescene
intensity of photoexcited TPT* Fig. S-1, S-2, S-3, and S-4 in SI).
Meanwhile, the UV-visible spectrum of 4-methoxystyrene (1a
system, and found arylalkylketones 5a (83%) and 5b (49%)
could be obtained through tandem enamine-ketoimine
isomerization and hydrolysis.
(
)
displayed a maximum absorption at around 220-320 nm (Fig.
S-5 in SI). Although the emission spectrum (420-600 nm) of
TPT photocatalyst which was irradiated by 410 nm light (see
Fig. S-6), was not overlapped with the UV-absorption spectrum
of 1a, when the TPT catalyst was irradiated by 490, 500, and
520 nm, respectively, a new emission spectrum at around 290-
330 nm from TPT was observed (Fig. S-7). The partial overlap
between the UV-absorption spectrum (around 220-320 nm) of
1a and the emission spectrum (290-330 nm) of TPT indicated
that the energy transfer process from excited TPT* to
vinylarenes possibly occurred in this Markovnikov
hydroamination.
Scheme 3. Alkene scope a, b
Scheme 4. Preliminary mechanistic studies
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experiments were performed under argon atmosphere.VSieowlvAertnictlesOwnelinree
treated with 4 Å molecular sieves or sodiumDaOndI: 1d0is.1t0il3l9ed/Cp9rOioBr02to45u7sCe.
Purifications of reaction products were carried out by flash
chromatography using silica gel (300-400 mesh). Infrared spectra
1
(IR) are reported as wavelength numbers (cm-1). H NMR and 13C
NMR spectra were recorded with tetramethylsilane (TMS) as
internal standard at ambient temperature unless otherwise indicated
on a Bruker Avance DPX 600 fourier Transform spectrometer
1
operating at 400 MHz or 500 MHz for H NMR and 100 MHz or
125 MHz for 13C NMR. Chemical shifts are reported in parts per
million (ppm) and coupling constants are reported as Hertz (Hz).
Splitting patterns are designated as singlet (s), broad singlet (bs),
doublet (d), triplet (t). Splitting patterns that could not be interpreted
or easily visualized are designated as multiple (m). Low resolution
mass spectra were recorded using a Waters HPLC/ZQ4000 Mass
Spectrometer. High resolution mass spectra (HR-MS) were recorded
on an IF-TOF spectrometer (Micromass). Gas chromatograph mass
spectra were obtained with a SHIMADZU model GCMS-QP5000
spectrometer..
The above-mentioned experiments, Stern-Volmer and spectral
analysis indicated that two reaction pathways were involved in this
transformation (Scheme 5). At first, the traditional Bronsted acid-
promoted Markovnikov hydroamination belongs to reaction
pathway A. Another reaction pathway B was involved in the visible-
light-assisted hydroamination, which started with the
photoexcitation of TPT to produce the excited state TPT*, then
TPT* activated styrene 1 and generate excited triplet styrene 1* via
EnT process. Meanwhile, the interaction of Bronsted acid (CF3CO2H)
with Ar2NH2 2 resulted in the formation of aminium ion Ar2NH3+ (2-
1a), whose proton could be captured by photoexcited styrene 1* to
produce benzylic carbocation species 1-1a through electrophilic
addition.13 Finally, the coupling reaction of carbocation species 1-1a
with arylamine 2 gave the Markovnikov hydroamination product 3
with the release of protons.
General Procedure for the Visivle-Light-Promoted Markovnikov
Hydroamination of Arylalkenes with Arylamines
A flame-dried Schlenk tube (25 mL) equipped with a magnetic
stirrer bar was charged sequentially with 0.1 mmol of styrenes 1, 0.2
mmol of arylamines 2, photo catalysts TPT (5 mol %), and
CF3CO2H (1.0 equiv) in TFE (1.0 mL) under air atmosphere. Then
the mixture was stirred and irradiated with 2 × 30 W blue LEDs at
room temperature for 10 h. The mixture was then filtered through a
short Celite pad. The filtrate was concentrated, and the product was
purified by column chromatography on silica gel (hexanes/ethyl
acetate) to afford the desired products 3.
4-Chloro-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1a)14: Yellow
oil, 21.2 mg, 81% yield (without TPT, 14.9 mg, 49% yield); 1H
NMR (400 MHz, CDCl3) δ 7.16 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 8.6
Hz, 2H), 6.77 (d, J = 8.5 Hz, 2H), 6.34 (d, J = 8.6 Hz, 2H), 4.31 (q, J
= 6.6 Hz, 1H), 3.70 (s, 3H), 1.40 (d, J = 6.6 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 158.6, 145.9, 136.7, 128.9, 126.9, 121.8, 114.5,
114.1, 55.3, 53.0, 24.9; MS(ESI): m/z = 261.1 [M+], IR (KBr): 3415,
2963, 2927, 2835, 1599, 1510, 1499, 1247, 1177, 815, 749 cm-1.
Scheme 5. The possible reaction mechanism
4-Fluoro-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1b): Yellow oil,
17.4 mg, 71% yield (without TPT, 6 mg, 24% yield); 1H NMR (400
MHz, CDCl3) δ 7.18 (d, J = 8.1 Hz, 2H), 6.78 (d, J = 8.5 Hz, 2H),
6.71 (t, J = 8.7 Hz, 2H), 6.35 (dd, J = 8.8, 4.4 Hz, 2H), 4.29 (q, J =
6.6 Hz, 1H), 3.70 (s, 3H), 1.40 (d, J = 6.7 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 158.6, 156.8 (d, J = 233.3 Hz), 143.7, 137.1(d, J =
1.4 Hz), 126.9, 115.6 (d, J = 22.1 Hz), 114.2(d, J = 7.3 Hz), 114.1,
55.3, 53.5, 25.1; 19F NMR (376 MHz, CDCl3) δ -128.32; HR-MS
(ESI) calcd for [M + 1]+: C15H17FNO: 246.1289, found: 246.1289;
IR (KBr): 3423, 2963, 2836, 1612, 1510, 1276, 1245, 1219, 820, 764,
750 cm-1.
4-Bromo-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1c)15: Yellow
oil, 22.3 mg, 73% yield (without TPT, 7.6 mg, 25% yield); 1H NMR
(400 MHz, CDCl3) δ 7.15 (d, J = 8.5 Hz, 2H), 7.06 (d, J = 8.7 Hz,
2H), 6.77 (d, J = 8.5 Hz, 2H), 6.29 (d, J = 8.7 Hz, 2H), 4.30 (q, J =
6.7 Hz, 1H), 3.87 (s, 1H, NH), 3.69 (s, 3H), 1.39 (d, J = 6.7 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 158.6, 146.3, 136.7, 131.8, 126.9,
Conclusions
In conclusion, we have developed a CF3CO2H/visible-light-
promoted reductive coupling-reaction between aryl alkenes
and arylamines for assembly of
approach is operationally simple and does not require any
metal catalysts, thus featuring highly regioselective
-arylalkyl amines. The present
a
Markovnikov addition. Furthermore, the control experiments
demonstrated that CF3CO2H and visible-light-catalysis play a
complementary role in producing carboncation intermediates.
Experimental Section
General Information
General Methods. All reactions were carried out in flame-dried
sealed tubes with magnetic stirring. Unless otherwise noted, all
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115.0, 114.1, 108.8, 55.3, 52.9, 25.0; MS(ESI): m/z = 305.0 [M+]; IR 2H), 6.90 (d, J = 8.6 Hz, 2H), 6.50 (d, J = 8.3 Hz, 2H), 4.47 (q, J =
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(KBr): 3415, 2962, 2927, 2834, 1593, 1510, 1496, 1246, 1177, 811, 6.6 Hz, 1H), 3.83 (s, 3H), 2.24 (s, 3H), 1.53D(Od,I:J10=.1063.79/HC9zO, 3BH02)4;5173CC
764, 750 cm-1.
NMR (100 MHz, CDCl3) δ 158.5, 145.1, 137.5, 129.6, 127.0, 126.4,
114.0, 113.6, 55.3, 53.1, 25.0, 20.4; MS(ESI): m/z = 241.2 [M+]; IR
(KBr): 3408, 2961, 2923, 2865, 2834, 1614, 1518, 1300, 1245, 1178,
1036, 830, 808, 750 cm-1.
4-Iodo-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1d): Yellow oil,
24.0 mg, 68% yield (without TPT, 19.4 mg, 55% yield); H NMR
(400 MHz, CDCl3) δ 7.32 (d, J = 7.5 Hz, 2H), 7.23 (d, J = 7.6 Hz,
1
2H), 6.85 (d, J = 7.5 Hz, 2H), 6.28 (d, J = 7.6 Hz, 2H), 4.39 (q, J = N-(1-(4-Methoxyphenyl)ethyl)-3-methylaniline (3-1j): Yellow oil,
1
6.6 Hz, 1H), 3.78 (s, 3H), 1.48 (d, J = 6.5 Hz, 3H); 13C NMR (100 15.9 mg, 66% yield (without TPT, 8.9 mg, 37% yield); H NMR
MHz, CDCl3) δ 158.6, 146.8, 137.6, 136.6, 126.8, 115.6, 114.1, 77.8, (400 MHz, CDCl3) δ 7.33 (d, J = 8.5 Hz, 2H), 7.03 (t, J = 7.7 Hz,
55.3, 52.8, 24.9; HR-MS (ESI) calcd for [M + 1]+: C15H17INO: 1H), 6.91 (d, J = 8.5 Hz, 2H), 6.53 (d, J = 7.4 Hz, 1H), 6.42 (s, 1H),
354.0349, found: 354.0343; IR (KBr): 2929, 2833, 1594, 1510, 1275, 6.37 (d, J = 8.1 Hz, 1H), 4.50 (q, J = 6.6 Hz, 1H), 3.83 (s, 3H), 2.27
1261, 1177, 832, 764, 750 cm-1.
(s, 3H), 1.53 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
158.5, 147.4, 138.8, 137.4, 129.0, 127.0, 118.2, 114.3, 114.0, 110.4,
55.3, 52.8, 24.9, 21.6; HR-MS (ESI) calcd for [M + 1]+: C16H20NO:
242.1539, found: 242.1535; IR (KBr): 3403, 2961, 2924, 2834, 1607,
1587, 1510, 1488, 1244, 1176, 1036, 830, 769, 692 cm-1.
3,4-Dichloro-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1e): Yellow
oil, 21.9 mg, 74% yield (without TPT, 7 mg, 24% yield); H NMR
(400 MHz, CDCl3) δ 7.22 (d, J = 8.1 Hz, 2H), 7.08 (d, J = 8.7 Hz,
1H), 6.86 (d, J = 8.1 Hz, 2H), 6.57 (s, 1H), 6.32 (d, J = 8.7 Hz, 1H),
1
4.37 (q, J = 6.5 Hz, 1H), 4.07 (s, 1H, NH), 3.78 (s, 3H), 1.47 (d, J = N-(1-(4-Methoxyphenyl)ethyl)-2-methylaniline (3-1k): Yellow oil,
1
6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.7, 146.8, 136.1, 7.0 mg, 29% yield (without TPT, trace yield); H NMR (400 MHz,
132.6, 130.5, 126.8, 119.7, 114.5, 114.2, 112.9, 55.3, 52.9, 24.8; CDCl3) δ 7.18 (d, J = 7.6 Hz, 2H), 6.95 (d, J = 7.2 Hz, 1H), 6.87 (t, J
HR-MS (ESI) calcd for [M + 1]+: C15H16Cl2NO: 296.0603, found: = 7.7 Hz, 1H), 6.76 (d, J = 7.6 Hz, 2H), 6.50 (t, J = 7.3 Hz, 1H), 6.30
296.0606; IR (KBr): 3419, 2963, 2928, 2835, 1597, 1511, 1492, (d, J = 8.0 Hz, 1H), 4.40 (q, J = 6.3 Hz, 1H), 3.71 (s, 1H, NH), 3.67
1320, 1244, 1175, 1132, 1036, 830, 808, 666 cm-1.
(s, 3H), 2.11 (s, 3H), 1.44 (d, J = 6.5 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 158.5, 145.3, 137.4, 130.0, 127.0, 126.9, 121.6, 116.8,
114.1, 111.1, 55.3, 52.7, 25.3, 17.7; HR-MS (ESI) calcd for [M + 1]+:
C16H20NO: 242.1539, found: 242.1537; IR (KBr): 3429, 2961, 2927,
2834, 1606, 1585, 1511, 1444, 1314, 1246, 1174, 1036, 829, 748 cm-
4-Chloro-N-(1-(4-methoxyphenyl)ethyl)-3-(trifluoromethyl)anili
ne (3-1f): Yellow oil, 20.1 mg, 61% yield (without TPT, 17 mg, 52%
yield); 1H NMR (400 MHz, CDCl3) δ 7.27 (d, J = 8.4 Hz, 2H), 7.17
(d, J = 8.7 Hz, 1H), 6.93 – 6.85 (m, 3H), 6.54 (d, J = 8.6 Hz, 1H),
4.45 (q, J = 6.2 Hz, 1H), 4.26 (s, 1H, NH), 3.82 (s, 3H), 1.53 (d, J =
1
.
6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.8, 145.8, 135.9, N-(1-(4-Methoxyphenyl)ethyl)-3,5-dimethylaniline (3-1l): Yellow
131.9, 126.8, 121.6, 118.7 (d, J = 2.2 Hz), 116.5, 114.3, 112.2 (q, J = oil, 19.2 mg, 75% yield (without TPT, 3.6 mg, 14% yield); 1H NMR
5.6 Hz), 55.3, 53.0, 24.8; HR-MS (ESI) calcd for [M + 1]+: (400 MHz, CDCl3) δ 7.20 (d, J = 8.1 Hz, 2H), 6.77 (d, J = 8.1 Hz,
C16H16ClF3NO: 330.0867, found: 330.0864; IR (KBr): 3412, 2964, 2H), 6.23 (s, 1H), 6.09 (s, 2H), 4.36 (q, J = 6.4 Hz, 1H), 3.70 (s, 3H),
2930, 2838, 1612, 1511, 1487, 1341, 1247, 1174, 1133, 1025, 830, 2.09 (s, 6H), 1.39 (d, J = 6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
814, 671 cm-1.
δ 158.5, 147.5, 138.7, 137.5, 127.0, 119.3, 114.0, 111.3, 55.3, 52.7,
24.9, 21.5; HR-MS (ESI) calcd for [M + 1]+: C17H22NO: 256.1696,
found: 256.1692; IR (KBr): 3401, 2960, 2922, 2856, 1603, 1510,
1338, 1244, 1180, 1035, 827, 749 cm-1.
4-Chloro-N-(1-(4-methoxyphenyl)ethyl)-3-nitroaniline
Yellow oil, 22.7 mg, 74% yield (without TPT, 15 mg, 49% yield);
1H NMR (400 MHz, CDCl3) δ 7.21 (d, J = 7.6 Hz, 2H), 7.15 (d, J =
(3-1g):
8.7 Hz, 1H), 6.95 (s, 1H), 6.86 (d, J = 7.6 Hz, 2H), 6.58 (d, J = 8.8 4-Ethyl-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1m): Yellow oil,
Hz, 1H), 4.41 (q, J = 5.3 Hz, 1H), 4.35 (s, 1H, NH), 3.78 (s, 3H), 16.8 mg, 66% yield (without TPT, 10 mg, 39% yield); 1H NMR (400
1.51 (d, J = 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 159.0, MHz, CDCl3) δ 7.35 (d, J = 8.3 Hz, 2H), 7.00 (d, J = 8.1 Hz, 2H),
148.4, 146.5, 135.3, 131.9, 126.8, 117.7, 114.4, 113.5, 109.2, 55.3, 6.92 (d, J = 8.4 Hz, 2H), 6.53 (d, J = 8.1 Hz, 2H), 4.48 (q, J = 6.6 Hz,
53.0, 24.6; HR-MS (ESI) calcd for [M + Na]+: C15H16ClN2NaO3: 1H), 3.84 (s, 3H), 2.56 (q, J = 7.6 Hz, 2H), 1.54 (d, J = 6.7 Hz, 3H),
329.0663, found: 329.0665; IR (KBr): 3412, 2964, 2929, 2836, 1611, 1.22 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.5, 145.4,
1533, 1511, 1332, 1246, 1176, 1035, 831, 817, 752, 685 cm-1.
137.6, 133.0, 128.5, 127.0, 114.0, 113.5, 55.3, 53.2, 27.9, 25.1, 15.9;
HR-MS (ESI) calcd for [M + 1]+: C17H22NO: 256.1696, found:
256.1694; IR (KBr): 3407, 2961, 2928, 2869, 1614, 1517, 1300,
1245, 1179, 1036, 827 cm-1.
N-(1-(4-Methoxyphenyl)ethyl)aniline (3-1h)16: Yellow oil, 15.2
1
mg, 67% yield (without TPT, 9.9 mg, 44% yield); H NMR (400
MHz, CDCl3) δ 7.24 – 7.17 (m, 2H), 7.04 (t, J = 7.4 Hz, 2H), 6.77 (d,
J = 7.9 Hz, 2H), 6.67 (t, J = 6.9 Hz, 1H), 6.57 (d, J = 7.4 Hz, 2H), N-(1-(4-Methoxyphenyl)ethyl)-4-propylaniline (3-1n): Yellow oil,
4.38 (q, J = 6.6 Hz, 1H), 3.70 (s, 3H), 1.49 (d, J = 6.5 Hz, 3H); 13C 17.8 mg, 66% yield (without TPT, 10.0 mg, 37% yield); 1H NMR
NMR (100 MHz, CDCl3) δ 158.6, 147.4, 137.3, 129.1, 127.0, 117.3, (400 MHz, CDCl3) δ 7.27 (d, J = 7.9 Hz, 2H), 6.90 (d, J = 7.7 Hz,
114.1, 113.4, 55.3, 52.9, 25.0; MS(ESI): m/z= 227.1 [M+]; IR (KBr): 2H), 6.84 (d, J = 8.0 Hz, 2H), 6.44 (d, J = 7.8 Hz, 2H), 4.40 (q, J =
3407, 2960, 2923, 2835, 1603, 1508, 1244, 1178, 1034, 830, 750, 6.5 Hz, 1H), 3.76 (s, 3H), 2.42 (t, J = 7.6 Hz, 2H), 1.55 (dt, J = 14.8,
693 cm-1.
7.4 Hz, 2H), 1.46 (d, J = 6.6 Hz, 3H), 0.89 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 158.5, 145.4, 137.6, 131.5, 129.1, 127.0,
114.0, 113.4, 55.3, 53.1, 37.2, 25.1, 24.9, 13.9; HR-MS (ESI) calcd
for [M + 1]+: C18H24NO: 270.1852, found: 270.1844; IR (KBr): 3409,
N-(1-(4-Methoxyphenyl)ethyl)-4-methylaniline (3-1i)17: Yellow
oil, 16.9 mg, 70% yield (without TPT, 7.5 mg, 31% yield); 1H NMR
(400 MHz, CDCl3) δ 7.33 (d, J = 8.5 Hz, 2H), 6.96 (d, J = 8.2 Hz,
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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
2958, 2927, 2869, 1614, 1515, 1301, 1244, 1179, 1037, 829, 750 cm- 4-(1-(4-Methoxyphenyl)ethyl)naphthalen-1-amine (V3ie-w1tA)r:ticYleeOlnlolinwe
1
1
DOI: 10.1039/C9OB02457C
.
oil, 20.0 mg, 72% yield (without TPT, 1.9 mg, 7% yield); H NMR
(400 MHz, CDCl3) δ 7.88 – 7.77 (m, 2H), 7.52 – 7.40 (m, 4H), 7.21
(d, J = 8.0 Hz, 2H), 6.87 (d, J = 7.9 Hz, 2H), 4.30 (q, J = 7.0 Hz, 1H),
4.11 (s, 2H, NH), 3.81 (s, 3H), 1.75 (d, J = 7.1 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 158.1, 138.8, 137.7, 133.1, 128.5, 125.8, 125.2,
124.9, 124.1, 123.8, 120.5, 118.4, 114.1, 55.3, 39.5, 21.9; HR-MS
(ESI) calcd for [M + 1]+: C19H20NO: 278.1539, found: 278.1540; IR
(KBr): 3460, 3387, 3057, 2963, 2930, 2834, 1621, 1509, 1400, 1245,
1178, 1031, 832, 803, 748 cm-1.
4-Butyl-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1o): Yellow oil,
17.3 mg, 61% yield (without TPT, 9.6 mg, 34% yield); H NMR
1
(400 MHz, CDCl3) δ 7.28 (d, J = 7.6 Hz, 2H), 6.90 (d, J = 7.5 Hz,
2H), 6.84 (d, J = 7.6 Hz, 2H), 6.44 (d, J = 7.4 Hz, 2H), 4.40 (q, J =
6.4 Hz, 1H), 3.77 (s, 3H), 2.44 (t, J = 7.5 Hz, 2H), 1.55 – 1.44 (m,
5H), 1.35 – 1.24 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 158.5, 145.3, 137.6, 131.6, 129.0, 127.0, 114.0,
113.4, 55.3, 53.1, 34.7, 34.0, 25.1, 22.4, 14.0; HR-MS (ESI) calcd
for [M + 1]+: C19H26NO: 284.2009, found: 284.2004; IR (KBr): 3409, N-Ethyl-4-(1-(4-methoxyphenyl)ethyl)aniline (3-1u): Yellow oil,
1
2958, 2927, 2869, 1614, 1515, 1301, 1244, 1179, 1037, 829, 750 cm- 14.0 mg, 55% yield (without TPT, 7.5 mg, 29% yield); H NMR
1
.
(400 MHz, CDCl3) δ 7.04 (d, J = 8.5 Hz, 2H), 6.93 (d, J = 8.3 Hz,
2H), 6.73 (d, J = 8.5 Hz, 2H), 6.47 (d, J = 8.4 Hz, 2H), 3.92 (q, J =
7.2 Hz, 1H), 3.70 (s, 1H, NH), 3.69 (s, 3H), 3.05 (q, J = 7.1 Hz, 2H),
1.48 (d, J = 7.2 Hz, 3H), 1.15 (t, J = 7.1 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 157.7, 146.5, 139.5, 135.8, 128.4, 128.3, 113.7,
112.9, 55.3, 43.1, 38.8, 22.3, 14.9; HR-MS (ESI) calcd for [M + 1]+:
C17H22NO: 256.1696, found: 256.1689; IR (KBr): 2963, 2920, 1611,
1510, 1245, 1177, 1033, 831, 749 cm-1.
4-Methoxy-N-(1-(4-methoxyphenyl)ethyl)aniline (3-1p)18: Yellow
oil, 19.0 mg, 74% yield (without TPT, 4.9 mg, 19% yield); 1H NMR
(400 MHz, CDCl3) δ 7.33 (d, J = 8.1 Hz, 2H), 6.91 (d, J = 8.2 Hz,
2H), 6.75 (d, J = 8.6 Hz, 2H), 6.53 (d, J = 8.5 Hz, 2H), 4.43 (q, J =
6.6 Hz, 1H), 3.83 (s, 3H), 3.74 (s, 3H), 1.52 (d, J = 6.6 Hz, 3H); 13
C
NMR (100 MHz, CDCl3) δ 158.5, 152.0, 141.6, 137.5, 127.0, 114.8,
114.7, 114.0, 55.8, 55.3, 53.7, 25.1; MS(ESI): m/z=257.1 [M+]; IR
(KBr): 3397, 2959, 2931, 2833, 1611, 1511, 1241, 1177, 1037, 820, N-(1-(4-Methoxyphenyl)ethyl)benzo[d][1,3]dioxol-5-amine (3-1v):
1
758 cm-1.
Yellow oil, 7.6 mg, 28% yield; H NMR (400 MHz, CDCl3) δ 7.25
(d, J = 7.6 Hz, 2H), 6.85 (d, J = 8.0 Hz, 2H), 6.56 (d, J = 8.3 Hz, 1H),
6.14 (s, 1H), 5.94 (d, J = 8.3 Hz, 1H), 5.78 (s, 2H), 4.34 (q, J = 6.4
Hz, 1H), 3.77 (s, 3H), 1.45 (d, J = 6.5 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 158.5, 148.1, 143.1, 139.4, 137.3, 126.9, 114.0, 108.5,
105.2, 100.5, 96.4, 55.3, 53.7, 25.1; HR-MS (ESI) calcd for [M + 1]+:
C16H18NO3: 272.1281, found: 272.1287; IR (KBr): 3410, 2961, 2921,
2850, 1633, 1611, 1504, 1488, 1285, 1244, 1210, 1178, 1038, 934,
831, 813, 789 cm-1.
N-(1-(4-Methoxyphenyl)ethyl)-[1,1'-biphenyl]-4-amine
(3-1q):
Yellow oil, 17.6 mg, 58% yield (without TPT, 8.5 mg, 28% yield);
1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.7 Hz, 2H), 7.34 (t, J =
7.0 Hz, 4H), 7.28 (d, J = 7.7 Hz, 2H), 7.24 – 7.17 (m, 1H), 6.85 (d, J
= 7.7 Hz, 2H), 6.56 (d, J = 7.6 Hz, 2H), 4.47 (q, J = 6.5 Hz, 1H),
4.06 (s, 1H, NH), 3.76 (s, 3H), 1.49 (d, J = 6.5 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 158.6, 146.9, 141.3, 137.2, 130.1, 128.7, 127.9,
127.0, 126.3, 126.0, 114.1, 113.6, 55.3, 52.9, 25.1; HR-MS (ESI)
calcd for [M + 1]+: C21H22NO: 304.1696, found: 304.1683; IR (KBr): 6-(1-(4-Methoxyphenyl)ethyl)benzo[d][1,3]dioxol-5-amine (3-1w):
3409, 3025, 2962, 2928, 2834, 1612, 1524, 1511, 1489, 1322, 1299, Yellow oil, 14.1 mg, 52% yield; 1H NMR (400 MHz, CDCl3) δ 7.10
1245, 1177, 1036, 827, 763, 698 cm-1.
(d, J = 7.9 Hz, 2H), 6.85 – 6.77 (m, 3H), 6.24 (s, 1H), 5.85 (s, 2H),
3.96 (q, J = 7.0 Hz, 1H), 3.76 (s, 3H), 3.24 (s, 2H, NH), 1.53 (d, J =
7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.1, 146.2 140.6,
138.6, 137.8, 128.3, 122.8, 114.1, 107.4, 100.6, 98.6, 55.3, 39.1,
22.2; HR-MS (ESI) calcd for [M + 1]+: C16H18NO3: 272.1281, found:
272.1281; IR (KBr): 3442, 3367, 2962, 2929, 2835, 1633, 1609,
1507, 1485, 1244, 1172, 1037, 932, 831, 750 cm-1.
N-(1-(4-Methoxyphenyl)ethyl)quinolin-8-amine (3-1r): Yellow oil,
11.4 mg, 41% yield (without TPT, 2.5 mg, 9% yield); 1H NMR (400
MHz, CDCl3) δ 8.78 (d, J = 2.1 Hz, 1H), 8.07 (d, J = 8.2 Hz, 1H),
7.39 (t, J = 9.0 Hz, 3H), 7.26 (t, J = 8.2 Hz, 1H), 7.02 (d, J = 8.1 Hz,
1H), 6.88 (d, J = 7.6 Hz, 2H), 6.58 (s, 1H, NH), 6.46 (d, J = 7.6 Hz,
1H), 4.66 (m, 1H), 3.80 (s, 3H), 1.70 (d, J = 6.9 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 158.5, 146.8, 143.7, 138.2, 137.2, 136.1, 128.6, 4-Chloro-N-(1-(3,4-dimethoxyphenyl)ethyl)aniline (3-2a): Yellow
127.7, 126.9, 121.3, 114.0, 113.9, 106.2, 55.3, 52.7, 25.2; HR-MS oil, 21.3 mg, 73% yield (without TPT, 14.9 mg, 51% yield); 1H
(ESI) calcd for [M + 1]+: C18H19N2O: 279.1492, found: 279.1490; IR NMR (400 MHz, CDCl3) δ 7.02 (d, J = 7.5 Hz, 2H), 6.87 (d, J =
(KBr): 3394, 2960, 2922, 2849, 1611, 1575, 1518, 1479, 1379, 1245, 10.3 Hz, 2H), 6.81 (d, J = 8.0 Hz, 1H), 6.42 (d, J = 7.5 Hz, 2H), 4.36
1172, 1035, 830, 818, 791, 747 cm-1.
(q, J = 6.5 Hz, 1H), 4.02 (s, 1H, NH), 3.84 (s, 6H), 1.48 (d, J = 6.5
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 149.3, 148.0, 145.9, 137.4,
128.9, 121.8, 117.7, 114.5, 111.4, 109.0, 55.9, 53.4, 25.0; HR-MS
(ESI) calcd for [M + 1]+: C16H19ClNO2: 292.1099, found: 292.1091;
IR (KBr): 3404, 2961, 2932, 2834, 1599, 1515, 1499, 1316, 1256,
1169, 1027, 814, 764 cm-1.
1-(1-(4-Methoxyphenyl)ethyl)indoline (3-1s): Yellow oil, 10.4 mg,
41% yield (without TPT, 7.3 mg, 29% yield); H NMR (400 MHz,
CDCl3) δ 7.36 (d, J = 7.8 Hz, 2H), 7.09 (d, J = 7.1 Hz, 1H), 7.04 (t, J
= 7.6 Hz, 1H), 6.91 (d, J = 7.7 Hz, 2H), 6.64 (t, J = 7.2 Hz, 1H), 6.42
(d, J = 7.8 Hz, 1H), 4.74 (q, J = 6.6 Hz, 1H), 3.84 (s, 3H), 3.40 (q, J
1
= 9.0 Hz, 1H), 3.31 (q, J = 7.8 Hz, 1H), 2.97 (t, J = 8.4 Hz, 2H), 1.55 N-(1-(4-(tert-Butyl)phenyl)ethyl)-4-chloroaniline (3-2b): Yellow
(d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.5, 151.5, oil, 22.2 mg, 77% yield (without TPT, 3.5 mg, 12% yield); 1H NMR
134.9, 130.2, 128.2, 127.2, 124.4, 116.9, 113.7, 107.2, 55.3, 53.8, (400 MHz, CDCl3) δ 7.39 (d, J = 7.3 Hz, 2H), 7.31 (d, J = 7.6 Hz,
47.8, 28.2, 16.4; HR-MS (ESI) calcd for [M + 1]+: C17H20NO: 2H), 7.09 (d, J = 7.6 Hz, 2H), 6.49 (d, J = 7.7 Hz, 2H), 4.48 (q, J =
254.1539, found: 254.1540; IR (KBr): 2963, 2930, 2834, 1607, 1512, 6.5 Hz, 1H), 4.08 (s, 1H, NH), 1.55 (d, J = 6.5 Hz, 3H), 1.37 (s, 9H);
1487, 1302, 1248, 1178, 1031, 832, 743 cm-1.
13C NMR (100 MHz, CDCl3) δ 149.9, 146.0, 141.6, 129.0, 125.6,
6 | J. Name., 2019, 00, 1-3
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125.5, 121.7, 114.4, 53.2, 34.5, 31.5, 24.8; HR-MS (ESI) calcd for 4-Chloro-N-(1-(4-methoxy-3-(trifluoromethyl)phenyl)ethyl)anili
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[M + 1]+: C18H23ClN: 288.1441, found: 288.1429; IR (KBr): 3418, ne (3-2h): Yellow oil, 18.8 mg, 57% yieldD(OwIi:th10o.u10t3T9P/CT9,O1B10.254m57gC,
3023, 2962, 2903, 2867, 1600, 1497, 1316, 1295, 1252, 1177, 1091, 35% yield); 1H NMR (400 MHz, CDCl3) δ 7.45 (s, 1H), 7.38 (d, J =
1015, 832, 814, 677, 576 cm-1.
8.5 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 8.5 Hz, 1H), 6.32
(d, J = 8.8 Hz, 2H), 4.33 (q, J = 6.6 Hz, 1H), 3.94 (s, 1H, NH), 3.80
(s, 3H), 1.41 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
156.5 (q, J = 1.7 Hz), 145.5, 136.5, 130.4, 129.0, 124.6 (q, J = 5.2
Hz), 122.2, 119.1, 114.5, 112.4, 56.0, 52.9, 25.0; 19F NMR (376
MHz, CDCl3) δ -62.30; HR-MS (ESI) calcd for [M + 1]+:
C16H16ClF3NO: 330.0867, found: 330.0867; IR (KBr): 3422, 2967,
2931, 2843, 1620, 1599, 1504, 1324, 1277, 1258, 1129, 1057, 1024,
817, 677 cm-1.
6-Chloro-4-(p-tolyl)-1,2,3,4-tetrahydroquinoline (3-2c): Yellow
oil, 7.7 mg, 30% yield (without TPT, 2.5 mg, 9% yield); H NMR
1
(400 MHz, CDCl3) δ 7.14 (d, J = 7.7 Hz, 2H), 7.03 (d, J = 7.7 Hz,
2H), 6.97 (d, J = 8.3 Hz, 1H), 6.75 (s, 1H), 6.48 (d, J = 8.5 Hz, 1H),
4.08 (t, J = 6.0 Hz, 1H), 3.34 – 3.21 (m, 2H), 2.36 (s, 3H), 2.23 –
2.14 (m, 1H), 2.08 – 1.99 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
143.4, 142.8, 136.0, 129.9, 129.2, 128.5, 127.2, 125.2, 121.5, 115.3,
42.3, 39.1, 30.7, 21.0; HR-MS (ESI) calcd for [M + 1]+: C16H17ClN:
258.1044, found: 258.1036; IR (KBr): 3415, 2922, 2851, 1601, 1496, 4-Chloro-N-(1-(4-methoxyphenyl)propyl)aniline (3-2i): Yellow
1353, 1297, 1263, 1084, 809, 765 cm-1.
oil, 12.4 mg, 45% yield (without TPT, 5.5 mg, 20% yield); 1H NMR
(400 MHz, CDCl3) δ 7.21 (d, J = 8.1 Hz, 2H), 7.00 (d, J = 8.2 Hz,
2H), 6.85 (d, J = 8.1 Hz, 2H), 6.42 (d, J = 8.3 Hz, 2H), 4.12 (t, J =
6.4 Hz, 1H), 4.04 (s, 1H, NH), 3.78 (s, 3H), 1.88 – 1.70 (m, 2H),
0.92 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 158.6, 146.1,
135.3, 128.9, 127.5, 121.6, 114.4, 114.0, 59.3, 55.3, 31.6, 10.8; HR-
MS (ESI) calcd for [M + 1]+: C16H19ClNO: 276.1150, found:
276.1155; IR (KBr): 3430, 2960, 2920, 2850, 1608, 1509, 1497,
1302, 1245, 1175, 1090, 1032, 814, 749 cm-1.
4-(1-((4-Chlorophenyl)amino)ethyl)phenol (3-2d): Yellow oil, 9.9
mg, 40% yield (without TPT, 2.5 mg, 10% yield); H NMR (400
1
MHz, CDCl3) δ 7.17 (d, J = 7.8 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H),
6.76 (d, J = 7.9 Hz, 2H), 6.41 (d, J = 8.0 Hz, 2H), 4.54 (s, 1H, NH),
4.37 (q, J = 6.6 Hz, 1H), 1.46 (d, J = 6.6 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 154.5, 145.8, 136.9, 128.9, 127.1, 121.8, 115.6,
114.5, 53.0, 25.0; HR-MS (ESI) calcd for [M + 1]+: C14H15ClNO:
248.0837, found: 248.0836; IR (KBr): 3589, 3450, 3022, 2965, 2925,
2868, 1612, 1598, 1512, 1497, 1316, 1252, 1176, 1092, 1012, 832, N-(4-Chlorophenyl)-5-methoxy-2,3-dihydro-1H-inden-1-amine
1
816, 739 cm-1.
(3-2j): Yellow oil, 6.8 mg, 25% yield (without TPT, 0% yield); H
NMR (500 MHz, CDCl3) δ 7.24 (d, J = 8.3 Hz, 1H), 7.16 – 7.14 (m,
1H), 7.13 – 7.11 (m, 1H), 6.81 (d, J = 2.0 Hz, 1H), 6.76 (dd, J = 8.3,
2.4 Hz, 1H), 6.63 – 6.61 (m, 1H), 6.61 – 6.59 (m, 1H), 4.90 (t, J =
6.3 Hz, 1H), 3.86 (s, 1H, NH), 3.80 (s, 3H), 3.04 – 2.95 (m, 1H),
2.91 – 2.81 (m, 1H), 2.60 – 2.50 (m, 1H), 1.96 – 1.86 (m, 1H); 13C
NMR (125 MHz, CDCl3) δ 160.1, 145.4, 136.2, 129.2, 124.9, 114.3,
112.9, 110.0, 58.1, 55.5, 33.9, 30.4; HR-MS (ESI) calcd for [M + 1]+:
4-Chloro-N-(1-(3-fluoro-4-methoxyphenyl)ethyl)aniline (3-2e):
Yellow oil, 19.0 mg, 68% yield (without TPT, trace yield); 1H NMR
(400 MHz, CDCl3) δ 7.09 – 7.00 (m, 4H), 6.90 (t, J = 8.5 Hz, 1H),
6.40 (d, J = 8.5 Hz, 2H), 4.36 (q, J = 6.5 Hz, 1H), 4.00 (s, 1H, NH),
3.86 (s, 3H), 1.47 (d, J = 6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ 146.4 (d, J = 10.7 Hz), 145.6, 138.0 (d, J = 4.9 Hz), 129.0, 122.1,
121.3 (d, J = 3.1 Hz), 114.4, 113.7 (d, J = 1.0 Hz), 113.6, 113.5, 56.4,
52.8, 25.0; HR-MS (ESI) calcd for [M + 1]+: C15H16ClFNO:
280.0899, found: 280.0896; IR (KBr): 3412, 2964, 2928, 2850, 1600,
1518, 1499, 1295, 1274, 1133, 1028, 815, 761 cm-1.
C16H17ClNO: 274.0985, found: 274.1000;
IR (KBr): 3444, 2955,
2921, 2849, 1645, 1494, 1467, 1399, 1303, 1256, 1176, 1089, 1032,
814, 747 cm-1.
4-Chloro-N-(1-phenylethyl)aniline (3-2k), 4-Chloro-N-(1-(4-
(trifluoromethyl)phenyl)ethyl)aniline (3-2l) and 4-Chloro-N-(1-
(4-chlorophenyl)ethyl)aniline (3-2m) could not be obtained
under our reaction conditions.
4-Chloro-N-(1-(3-chloro-4-methoxyphenyl)ethyl)aniline (3-2f):
Yellow oil, 12.7 mg, 43% yield (without TPT, 2.8 mg, 9% yield); 1H
NMR (400 MHz, CDCl3) δ 7.33 (s, 1H), 7.17 (d, J = 8.4 Hz, 1H),
7.02 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 8.4 Hz, 1H), 6.40 (d, J = 8.5 Hz,
2H), 4.35 (q, J = 6.6 Hz, 1H), 3.99 (s, 1H, NH), 3.86 (s, 3H), 1.45 (d, 1-(4-Methoxyphenyl)ethan-1-one (5a)19: Yellow oil, 12.5 mg, 83%
1
J = 9.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 154.0, 145.6, 138.0, yield (without TPT, 7 mg, 47% yield); H NMR (400 MHz, CDCl3)
129.0, 127.7, 125.0, 122.7, 122.0, 114.5, 112.3, 56.2, 52.8, 25.0; δ 7.93 (d, J = 7.9 Hz, 2H), 6.93 (d, J = 7.9 Hz, 2H), 3.87 (s, 3H),
HR-MS (ESI) calcd for [M + 1]+: C15H16Cl2NO: 296.0603, found: 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 196.8, 163.5, 130.6,
296.0606; IR (KBr): 3417, 2965, 2927, 2838, 1600, 1503, 1316, 130.4, 113.7, 55.5, 26.3; MS(ESI): m/z = 150.1 [M+]; IR (KBr):
1290, 1256, 1202, 1178, 1091, 1063, 1021, 814, 739 cm-1.
3339, 3003, 2960, 2932, 2840, 1676, 1599, 1576, 1510, 1358, 1258,
1172, 1028, 957, 834, 806, 592, 577, 564 cm-1.
N-(1-(3-Bromo-4-methoxyphenyl)ethyl)-4-chloroaniline (3-2g):
Yellow oil, 14.0 mg, 41% yield (without TPT, 8 mg, 24% yield); 1H 1-(4-Methoxyphenyl)propan-1-one (5b)19: Yellow oil, 8.0 mg, 49%
NMR (400 MHz, CDCl3) δ 7.51 (d, J = 1.9 Hz, 1H), 7.22 (dd, J = yield (without TPT, 4 mg, 15% yield); H NMR (400 MHz, CDCl3)
1
8.4, 1.9 Hz, 1H), 7.02 (d, J = 8.8 Hz, 2H), 6.83 (d, J = 8.4 Hz, 1H), δ 7.95 (d, J = 8.1 Hz, 2H), 6.93 (d, J = 8.2 Hz, 2H), 3.86 (s, 3H),
6.40 (d, J = 8.8 Hz, 2H), 4.35 (q, J = 6.6 Hz, 1H), 3.99 (s, 1H, NH), 2.95 (q, J = 7.0 Hz, 2H), 1.21 (t, J = 7.2 Hz, 3H); 13C NMR (100
3.86 (s, 3H), 1.47 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) MHz, CDCl3) δ 199.6, 163.3, 130.2, 130.0, 113.7, 55.4, 31.4, 8.5;
δ 154.9, 145.6, 138.5, 130.8, 129.0, 125.7, 122.1, 114.5, 112.2, MS(ESI): m/z = 164.1 [M+]; IR (KBr): 3339, 3004, 2963, 2934,
112.0, 56.3, 52.7, 25.0; HR-MS (ESI) calcd for [M + 1]+: 2850, 1676, 1600, 1576, 1510, 1417, 1359, 1258, 1170, 1028, 959,
C15H16BrClNO: 340.0098, found: 340.0081; IR (KBr): 3415, 2963, 832, 807, 590, 578, 560 cm-1.
2927, 2838, 1600, 1497, 1315, 1286, 1255, 1053, 1020, 814, 736,
680, 552 cm-1.
Acknowledgements
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ARTICLE
Journal Name
This project has received funding from the NKRDPC (No.
2016YFA0602900, 2017YFC1703802), NFSC (No. 201871097,
U1801287), GPSF (No. 2017B090903003) and GNFS (No.
2018B030308007).
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7873.
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Beletskaya, Mendeleev Commun. 2014, 24, 332.
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Li, Y. Li, Eur. J. Org. Chem. 2012, 28, 5564.
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13 It should be noted when our work is almost done, Zhang
reported
a
visible-light/Cu(I)
system-catalyzed
intermolecular hydroamination of alkenes with amines via
8 | J. Name., 2019, 00, 1-3
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DOI: 10.1039/C9OB02457C
Organic & Biomolecular Chemistry
PAPER
Bronsted Acid/Visible-Light-Promoted Markovnikov
Hydroamination of Vinylarenes with Arylamines
Received 00th January 20xx,
Accepted 00th January 20xx
Jiao Gui,Haisheng Xie, Fengjuan Chen, Zhipeng Liu, Xiaoqi Zhang, Fubin Jiang, and Wei Zeng *
DOI: 10.1039/x0xx00000x
www.rsc.org/
Table of Content
A Bronsted acid/visible-light-promoted Markovnikov hydroamination of arylalkenes with arylamines in the
presence of TPT and CF3CO2H has been developed.
Bronsted acids
TPT
NHAr2
catalysts
visible-light
R
R
+
Ar2NH2
33 examples
(
)
Ar1
Ar1
Markovnikov regioselectivity
Metal-free
Markovnikov hydroamination
This journal is © The Royal Society of Chemistry 20xx
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