Ruthenium-catalyzed C-H allylation of arenes with allylic amines

Article abstract of DOI:10.1039/c8ob00723c

The Ru-catalyzed pyridyl-directed C-H allylation of arenes with allylic amines has been developed. This reaction was carried out in the presence of 5 mol% of [Ru(p-cymene)Cl₂]₂ and 0.5 equiv. of AgOAc in CF₃CH₂O

Full text of DOI:10.1039/c8ob00723c

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Ruthenium-Catalyzed C−H Allylation of Arenes with Allylic Amines
Rui Yana and Zhong-Xia Wang*,a,b
Received 00th January 20xx,
Accepted 00th January 20xx
The Ru-catalyzed pyridyl-directed C−H allylation of arenes with allylic amines has been developed. The reaction was
carried out in the presence of 5 mol % of [Ru(p-cymene)Cl2]2 and 0.5 equiv. of AgOAc in CF3CH2OH at 75 °C, affording
allylated products of arenes in moderate to excellent yields. The method exhibits a wide scope of allylic amines and arenes
and shows good compatibility of functional groups. Pyrazolyl- and pyrimidyl-directed C−H allylation of arenes were also
performed under the same conditions.
DOI: 10.1039/x0xx00000x
www.rsc.org/
using allylic halides, allylic alcohols and their derivatives have
been carried out.2-5 Inspired by previous work, we initiated a
study of transition-metal-catalyzed allylation of arenes with
Introduction
The allyl group is a prominent structural motif found in many
natural products and bioactive molecules. The compounds
containing allyl moiety are also versatile building blocks in
organic synthesis.1 Therefore, allylation reactions have
attracted much attention and a number of allylation methods
have been developed.1,2 Allylic surrogates used in various
allylation reactions include allylic halides,3 allylic alcohol4 or its
derivatives,5 allenes,6 1,3-dienes,7 and so on. Compared with
above the allylation agents, allylic amines have rarely been
allylic amines via C
report the results.
−H and C−N bond activation. Herein, we
Results and discussion
We commenced screening of reaction conditions by employing
reaction of 2-phenylpyridine (1a) with N-allyl-N-methylaniline
(
2a) as the model reaction. The catalyst systems for Ni- or Pd-
employed due to the stability of the C−
N bond.2g However, it
catalyzed allylic alkylation of carbonyl compounds were
demonstrated to be ineffective to our reaction.9c,9e Ruthenium
would be worthwhile to explore the reactions with allylic
amines from the perspective of understanding their reactivity
and finding novel allylation agents. Some successful trials have
been carried out.8,9 For example, Trost and Spagnol developed
a Ni-catalyzed cross-coupling of organoboronic acids with
allylamines with high regioselectivity in 1995.9a In 2007, List’s
was reported to catalyze the
arenes5a,10 and the C N bond cleavage of allylic amines.11
C−H functionalization of
−
Hence we tried to use ruthenium complex [Ru(p-cymene)Cl2]2
as the catalyst. The reaction of 1a with 2 equiv. of 2a in MeOH
at 75 °C in the presence of [Ru(p-cymene)Cl2]2 (5 mol %) and
AgOAc (1.0 equiv.) resulted in a mixture of 3aa (26%) and 3aa’
(16%) after 12 h (Table 1, entry 1). The positive result
encouraged us to further examine the reaction in different
solvents. The use of both EtOH and i-PrOH as solvents also led
to positive results and the latter exhibited better selectivity
(entries 2 and 3 in Table 1). However, use of aprotic solvents
involving toluene, THF and DMF gave negative results (entries
4-6 in Table 1). This experimental fact might imply that the
group reported
aldehydes catalyzed by palladium-based catalysts.9b In 2011
Zhang et al. performed a Pd-catalyzed -allylation of carbonyl
a highly enantioselective α-allylation of
α
compounds by reaction of allylic amines with ketones and
aldehydes.9c Recently Huang and co-workers reported a new
method for the formation of β,γ-unsaturated amides by Pd-
catalyzed carbonylation of allylamines via
activation.9d On the other hand,
activation and
functionalization represent an atom-economic transformation.
A series of C H allylation reactions of unreactive systems by
C−N bond
C−H
reaction was promoted via
a hydrogen bond-assisted
activation as that in Pd-catalyzed allylic alkylation of carbonyl
compounds.9c CF3CH2OH was found to be a better solvent than
the alcohols mentioned above and the reaction in CF3CH2OH
gave 3aa in 52% yield (entry 7 in Table 1). (CF3)2CHOH
exhibited poorer efficiency compared with CF3CH2OH. The
reaction in (CF3)2CHOH led to a mixture of 3aa (40%) and 3aa’
(10%) (entry 8 in Table 1). Hence the further condition
screenings were performed in CF3CH2OH. Increasing loading of
allylic amine markedly enhanced the product yield. Employing
4 equiv. of allylic amine gave excellent reaction result and
−
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Table 1 Optimization of reaction conditionsa
0.5 equiv of AgOAc loading was optimal (entries 15-17 in Table
1). The effect of temperature was next tested. Higher
temperature than 75 °C did not enhance the product yield and
lower temperature than 75 °C led to decrease of the yield
(entries 18 and 19 in Table 1). Other bases including KOAc,
AgOTf, Ag2O, and AgF were also tested (entries 20-23 in Table
1). KOAc was a good base but less effective than AgOAc.
AgOTf, Ag2O, and AgF led to a mixture of 3aa and 3aa’ in
relatively low yields. In the absence of a base the reaction still
occurred and gave a mixture of 3aa (5%) and 3aa’ (35%) in
relatively low overall yield (entry 24 in Table 1). In the absence
of a Ru catalyst the reaction cannot occur (entry 25 in Table 1).
Me
N
N
N
N
Ph (2a)
+
[Ru(p-cymene)Cl2]2 (5 mol%)
base, solvent, 75 °C, 12 h
3aa'
1a
3aa
Entry
Base (equiv.)
2a (equiv.)
solvent
yield (%)b
3aa (3aa’)
26 (16)
1
2
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1.5)
AgOAc (0.5)
AgOAc (0.2)
AgOAc (0.5)
AgOAc (0.5)
KOAc (1)
2
2
2
2
2
2
2
2
3
4
5
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
MeOH
EtOH
16 (26)
29 (0)
−
Other
Ru
complexes
including
RuH2(CO)(PPh3)3,
3
i-PrOH
Cp*Ru(PPh3)2Cl, [Cp*RuCl]4 and RuCl2(PPh3)3 were also
noneffective or less effective than [Ru(p-cymene)Cl2]2 (Table
S1 in the ESI). Finally, the optimized conditions were
demonstrated to suit for the reaction with a larger scale of
substrates. 0.4 Mmol of 1a was treated with 4 equiv. of 2a
under the optimized conditions to afford 3aa in 88% yield
(entry 26 in Table 1).
4
Toluene
5
THF
−
6
DMF
−
7
CF3CH2OH
(CF3)2CHOH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
52 (0)
40 (10)
80 (0)
86 (0)
88 (0)
78 (14)
74 (0)
85 (0)
80 (0)
90 (0)
79 (0)
91 (0)
83 (0)
81 (0)
8 (30)
3 (41)
7 (29)
5 (35)
−
8
9
Next, we examined reaction of 2-phenylpyridine (1a) or 2-
(o-tolyl)pyridine (1b) with different allylic amines under the
optimized conditions and the results are listed in Table 2. N-
10
11
12c
13d
14e
15
16
17
18f
19g
20
21
22
23
24
25h
26i
Allyl-N-phenylaniline
and
N-allyl-N-phenylhydroxylamine
reacted with 1a to afford 2-(2,6-diallylphenyl)pyridine (3aa) in
72% and 38% yield, respectively (entries 2 and 3 in Table 2).
Reaction of 2-(o-tolyl)pyridine (1b) with various allylic amines
resulted in ortho-monoallylation species. In this case 2 equiv.
of allylic amine was enough to complete the reaction. N-Allyl-
N-methylaniline still exhibited good reactivity. Its reaction with
1b gave 2-(2-allyl-6-methylphenyl)pyridine (3ba) in 88% yield
(entry 4 in Table 2). Other phenyl allylamines including N-allyl-
N-phenylaniline, N-allyl-N-phenylhydroxylamine, N,O-diallyl-
N-phenylhydroxylamine, N-allylaniline, and N,N-diallylaniline
reacted smoothly with 1b to form 3ba in 63%-92% yields
(entries 5-9 in Table 2). It is noteworthy that N-allylaniline
showed excellent reactivity in this transformation. Aliphatic
allylic amines can also be used in this transformation. Reaction
of 4-allylmorpholine with 1b at 50 °C afforded 3ba in 73%
yield, which was higher than that obtained from the reaction
at 75 °C (entry 10 in Table 2). Reaction of 1b with either N-
(but-3-en-2-yl)-N-methylaniline or (E)-N-(but-2-en-1-yl)-N-
methyl-aniline gave high overall yields. But in each case a
mixture of regio- and geo-isomers was obtained (entries 11
and 12 in Table 2).
AgOTf (0.5)
Ag2O (0.5)
AgF (0.5)
none
AgOAc (0.5)
AgOAc (0.5)
88 (0)
a Unless otherwise specified, the reactions were carried out on a 0.2 mmol scale
according to the conditions indicated by above equation. b Isolated yield. 2.5
c
mol % [Ru(p-cymene)Cl2]2 was employed. d Reaction time was 6 h. e Reaction time
To further examine the versatility of the reaction, we
evaluated the scope of 2-arylpyridines using N-allyl-N-
methylaniline (2a) as the allylation reagent. The results are
summarized in Schemes 1 and 2, respectively. Compound 2a
reacted smoothly with electron-poor 2-arylpyridines including
2-(2-FC6H4)C5H4N, 2-(2,4-F2C6H3)C5H4N, 2-(2-ClC6H4)C5H4N, 2-
(2-BrC6H4)C5H4N, and 2-(2-CF3C6H4)C5H4N to give the
g
was 24 h. f Reaction was run at 100 °C. Reaction was run at 50 °C. h No [Ru(p-
cymene)Cl2]2 was employed. i The reaction was on a 4 mmol scale.
higher loading of allylic amine did not markedly increase the
product yield (entries 9-11 in Table 1). Lowering the amount of
[Ru(p-cymene)Cl2]2 to 2.5 mol % resulted in decrease of 3aa
yield along with formation of 3aa’ in 14% yield (entry 12 in
Table 1). If the reaction time was shortened to 6 h the yield of
3aa decreased to 74%. However, extending reaction time to 24
h did not increase the product yield (entries 13 and 14 in Table
1). Next, we examined the effect of AgOAc dosage and found
corresponding monoallylation products (3ca−3ga, Scheme 1)
in moderate to good yields. Among the substrates 2-(2-
ClC6H4)C5H4N showed higher reactivity. Both 2-(2-FC6H4)C5H4N
and 2-(2,4-F2C6H3)C5H4N displayed relatively low reactivity.
2 | J. Name., 2012, 00, 1-3
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Part of the substrates remained unchanged. Under stronger of excess allylic amine, affording the corresponding products in
conditions, reaction of 2-(2,4-F2C6H3)C5H4N got improved to
moderate yields (3ha-3ja, Scheme 1). Some starting materials
Table 2 Scope of allylic aminesa
Entry
1c
Allylic amine
Product
Yield (%)b
90
3aa
2c
3c
3aa
3aa
72
38
4
88
3ba
5
6
3ba
3ba
68
63
Scheme 1 Monoallylation of of 2-arylpyridines. a Unless otherwise specified, the
reactions were carried out on a 0.2 mmol scale according to the conditions
7
3ba
38
b
indicated by the above equation, 2 equiv. of allylic amines were employed.
c
Yields of isolated products are reported. 4 Equiv. of allylic amines were
NHPh
employed. d The reaction was run at 100 °C for 18 h in the presence of 7.5 mol %
8
9
3ba
3ba
92
65
[Ru(p-cymene)Cl2]2.
remained unchanged. Both 2-(naphthalen-2-yl)pyridine and 2-
(naphthalen-1-yl)pyridine also respectively reacted with 2a
under the standard conditions. The former gave
10d
11
3ba
73
88e
monoallylation product 2-(3-allylnaphthalen-2-yl)pyridine (3ka
,
Scheme 1) in 51% yield, and the latter led to 2-(2-
allylnaphthalen-1-yl)pyridine (3la, Scheme 1) in 85% yield.
Reaction of the 2-(4-substituted phenyl)pyridines with 2a
under the standard conditions resulted in bisallylation
products
(3ma-3wa, Scheme 2). The para-substituents
included electron-donor groups such as Me, Ph, OMe, and OH
and electron-withdrawing groups such as F, Cl, Br, COOEt,
COOH, CF3 and NO2. Reaction of the substrates except 2-(4-
nitrophenyl)pyridine gave good yields. It seems that the
reactivity of the substrates is uncorrelated with the electron
effect of the substituents at the para position of the phenyl
rings. However, reaction of 2-(4-nitrophenyl)pyridine gave
relatively low product yield (45%) for unclear reasons.
Surprisingly, respective reaction of 2-(3-methoxyphenyl)-
pyridine, 2-(3-fluorophenyl)pyridine and 2-(3-chlorophenyl)-
12
82e
a Unless otherwise specified, the reactions were carried out on a 0.2 mmol scale
according to the conditions indicated by above equation, 2 equiv. of allylic
pyridine with 2a afforded bis-allylation products (3xa-3za,
Scheme 2) in moderate to good yields. This is probably due to
relatively small hindrance of these groups on the phenyl rings.
In addition, the catalyst system also suited for the
bisallylation of arenes with other directing groups such as
pyrazolyl group and pyrimidyl group. For example, reaction of
1-phenyl-1H-pyrazole with 2a under the standard conditions
b
c
amines were employed. Isolated yield.
employed. d The reaction was run at 50 °C. e Yield of the mixture.
4 equiv. of allylic amines were
some extent. 2-m-Tolylpyridine, 2-(3,4-dimethylphenyl)
pyridine, and 2-(biphenyl-3-yl)pyridine occurred ortho-C-H
monoallylation at the less hindered sites even in the presence
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gave 1-(2,6-diallylphenyl)-1H-pyrazole
(4) in 69% yield. 2-phenylpyridine in the presense of AgOAc (0.5 equiv.) in
Reaction of 2-phenylpyrimidine with 2a under the standard CF3CH2OH at 60 °C for 6 hours yielded ruthenium(II) complex
6
conditions afforded 2-(2,6-diallylphenyl)pyrimidine (
yield (Scheme 3).
5) in 78% (a in Scheme 4). Structure of the complex was confirmed by
comparing its spectroscopic data with those reported in
literature.12 No reaction occurred between [Ru(p-cymene)Cl2]2
and N-allyl-N-methylaniline under the same conditions.
Complex
N-methylaniline in the presence of AgOAc (0.5 equiv.) to afford
3aa in 29% yield (b in Scheme 4). Complex was also
6 was demonstrated to react with 4 equiv. of N-allyl-
6
demonstrated to catalyze reaction of 1a or 1b with 2a under
the optimized conditions to give the corresponding products in
similar yields to those employing [Ru(p-cymene)Cl2]2 as the
catalyst (c in Scheme 4 and section 3.3 in the ESI). These
experimental facts suggest that the cyclometalated complex
could be an intermediate in the catalytic cycle. Furthermore,
we measured the kinetic isotopic effect via reaction of 1a and
1a-D5 with 2a under the standard conditions. A kH/kD value of
1.1 was obtained by analyzing 1H NMR spectrum of the
2-Py
2-Py
2-Py
OMe
Ph
3ma (86%)
3na (74%)
3oa (83%)
2-Py
2-Py
2-Py
product (d in Scheme 4). This result suggests that the C−H
OH
bond cleavage may not be the rate-limiting step. As mentioned
earlier, reaction of 2-(o-tolyl)pyridine with either N-(but-3-en-
2-yl)-N-methylaniline or (E)-N-(but-2-en-1-yl)-N-methylaniline
resulted in a mixture of regio- and geo-isomers (entries 11 and
F
Cl
3pa (72%)
3ra (71%)
3qa (65%)
2-Py
2-Py
2-Py
12 in Table 2). This experimental fact implies that an η3
-
allylruthenium intermediate is present in the catalytic cycle.
The almost same distribution ratios of the products in the two
reactions further proved that the same η3-allylruthenium
intermediates were formed. In addition, the catalytic reaction
cannot occur in the aprotic solvents such as toluene, THF and
DMF but proceeded in alcohols including MeOH, EtOH, iPrOH,
(CF3)2CHOH and CF3CH2OH (Table 1). We surmised that the
Br
COOEt
3ta (81%)
COOH
3sa (65%)
3ua (71%)
2-Py
2-Py
CF3
NO2
3wa (45%)
3va (69%)
protic solvents promote the C−N bond cleavage of allylic
amines via a hydrogen-bond-activation.9c
2-Py
2-Py
2-Py
a
F
Cl
MeO
N
N
AgOAc (0.5 equiv.)
3xa (80%)
3ya (82%)
3za (58%)
[Ru(p-cymene)Cl2]2
+
Ru
CF3CH2OH, 60 °C, 6 h
Cl
Scheme 2 Bisallylation of 2-arylpyridines. a The reactions were carried out on a 0.2
mmol scale according to the conditions indicated by above equation, 4 equiv. of allylic
amines were employed. b Yields of isolated products are reported.
10 equiv.
6
Me
b
c
AgOAc (0.5 equiv)
CF3CH2OH, 75 °C, 12 h
N
6
+
3aa
Ph
29% yield
4 equiv.
[Ru(p-cymene)Cl2]2 (5 mol %)
N
N
Me
N
N
N
AgOAc (0.5 equiv.)
+
Ph
CF3CH2OH, 75 °C,12 h
Me
N
6 (10 mol %)
2a
N
3aa
89% yield
+
Ph
AgOAc (0.5 equiv.)
4 (69%)
CF3CH2OH, 75 °C, 12 h
4 equiv
Me
[Ru(p-cymene)Cl2]2 (5 mol %)
Me
N
d
N
N
N
N
AgOAc (0.5 equiv.)
N
Ph
standard conditions
N
+
N
Ph
N
CF3CH2OH, 75 °C,12 h
D
D
D
D
+
2a
KH/KD = 1.1
5 (78%)
H3/D3
D
Scheme 3 pyrazolyl- and pyrimidyl-directed bisallylation reaction.
Scheme 4 Preliminary mechanistic study.
To probe the reaction mechanism, we made the following
experiments. Reaction of [Ru(p-cymene)Cl2]2 with 10 equiv. of
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On the basis of above experimental results and literature
report,11a,13 we propose a plausible mechanism for the C
allylation (Scheme 5). The formation of active catalyst
action of [Ru(p-cymene)Cl2]2 with AgOAc. Coordination of the
pyridine group of compound 1a to and then ortho-phenyl
H bond activation form five-membered ring ruthenium
intermediate . Reaction of complex with the hydrogen-
bond-activated 2a affords an η3-allyl complex
. Reductive
elimination of results in 3aa′ and regenerates active catalyst
in the presence of OAc−. 3aa is formed from 3aa′ via the
Experimental
−
by
H
All reactions were performed under nitrogen atmosphere
using standard Schlenk and vacuum line techniques. Toluene
and THF were purified by JC Meyer Phoenix Solvent Systems.
DCE was dried over CaH2 and distilled under nitrogen. DMSO
and DMF were dried over 4 Å molecular sieve, fractionally
distilled under reduced pressure and stored under nitrogen.
CF3CH2OH was dried over 4 Å molecular sieve and distilled
under nitrogen. MeOH and EtOH were treated with Mg and
then distilled under nitrogen. [Ru(p-cymene)Cl2]2 was
purchased from TCI (Shanghai) Development Co., Ltd. 2-
Arylpyridines13 and allylic amines9c,14 were synthesized
according to the reported methods. All other chemicals were
obtained from commercial vendors and used as received. NMR
A
A
C
−
6
6
B
B
A
same pathway as for 3aa′
.
spectra were recorded on
a Bruker Avance III 400
spectrometer at ambient temperature. The chemical shifts of
the 1H NMR spectra were referenced to TMS or internal
solvent resonances and the chemical shifts of the 13C NMR
spectra were referenced to internal solvent resonances. The
chemical shifts of the 19F NMR spectra were referenced to
external CF3COOH. High-resolution mass spectra (HR-MS) were
acquired in the ESI mode using an Orbitrap mass analyzer.
Synthesis of 2-(3-fluorophenyl)pyridine and 2-(3-chlorophenyl)-
pyridine
2-(3-Fluorophenyl)pyridine and 2-(3-chlorophenyl)pyridine
were synthesized according to the reported method.13a
2-(3-Fluorophenyl)pyridine. 1H NMR (400 MHz, CDCl3): δ 8.68
(d, J = 4.7 Hz, 1H), 7.81–7.64 (m, 4H), 7.47–7.36 (m, 1H), 7.28–
7.19 (m, 1H), 7.09 (dt, J = 8.4, 2.2 Hz, 1H). 13C NMR (101 MHz,
CDCl3): δ 163.38 (d, J = 246.3 Hz), 156.08 (d, J = 2.7 Hz), 149.82
, 141.77 (d, J = 7.6 Hz), 136.95 , 130.29 (d, J = 8.2 Hz), 122.73,
122.47 (d, J = 2.8 Hz), 120.63 , 115.85 (d, J = 21.3 Hz), 113.93
(d, J = 22.8 Hz). 19F NMR (376 MHz, CDCl3): δ –112.91. HR-MS:
m/z 174.0705 [M+H]+, calcd for C11H9NF 174.0714.
Scheme 5 Proposed catalytic cycle.
2-(3-Chlorophenyl)pyridine. 1H NMR (400 MHz, CDCl3): δ 8.69
(d, J = 4.7 Hz, 1H), 8.01 (s, 1H), 7.89–7.82 (m, 1H), 7.75 (dt, J =
7.7, 1.6 Hz, 1H), 7.69 (d, J = 7.9 Hz, 1H), 7.43–7.35 (m, 2H),
7.28–7.21 (m, 1H). 13C NMR (101 MHz, CDCl3): δ 156.03,
149.88, 141.25, 137.01, 134.95, 130.07, 129.03, 127.20,
125.04, 122.77, 120.68. HR-MS: m/z 190.0408 [M+H]+, calcd
for C11H9NCl 190.0418.
Conclusions
In summary, a Ru-catalyzed method for allylation of arenes via
cleavage of the C N bond of allylic amines and pyridyl-directed
aryl C H activation has been developed. The reaction
−
−
proceeded under mild conditions and afforded the allylation
products in moderate to high yields. For 2-phenylpyridine and
2-(4-substituted phenyl)pyridines the reaction resulted in
ortho-position bisallylation products of the phenyl groups. For
the 2-(3-substituted phenyl)pyridines the reaction gave either
monoallylation or bisallylation products depending on the
steric hindrance of the 3-substituents. A range of functional
groups including electron-withdrawing and electron-donor
groups on the phenyl rings can be tolerated. Various
allylamines including aromatic amines, aliphatic amines, and
hydroxylamines were demonstrated to suit for this
transformation. The reaction is proposed to proceed via a
General procedure for the allylation of arenes with allylic amines
2-Arylpyridines (0.2 mmol), allylic amines (2 or 4 equiv.),
AgOAc (0.5 equiv.), [Ru(p-cymene)Cl2]2 (5 mol %), and
CF3CH2OH (1.5 cm3) were successively added into a Schlenk
tube. The mixture was stirred at 75 °C for 12 hours. Upon
cooling to room temperature, the resulting mixture was
diluted with EtOAc and filtered through a short pad of silica
gel. The filtrate was concentrated under reduced pressure and
the residue was purified by column chromatography to afford
the desired product.
hydrogen-bond-promoted C−N bond cleavage of the allyl
amines and a Ru(II)/Ru(IV) catalytic cycle.
2-(2,6-Diallylphenyl)pyridine (3aa). Elution with EtOAc/
petroleum ether 1/20 (v/v), colorless oil, yield 42.4 mg (90%).
1H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 4.1 Hz, 1H), 7.70 (t, J =
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7.6 Hz, 1H), 7.33–7.21 (m, 3H), 7.16 (d, J = 7.6 Hz, 2H), 5.88- CDCl3): δ 158.63, 149.45, 140.93, 140.56, 136.47, 136.17,
5.70 (m, 2H), 4.91 (d, J = 10.0 Hz, 2H), 4.80 (d, J = 17.0 Hz, 2H), 130.60, 129.62, 128.57, 125.26, 123.36, 122.53, 116.19, 38.27.
3.23–3.00 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 159.03, HR-MS: m/z 274.0213 [M+H]+, calcd for C14H13BrN 274.0226.
149.49, 140.09, 138.06, 137.36, 135.91, 128.35, 127.40, 2-(2-Allyl-6-(trifluoromethyl)phenyl)pyridine (3ga). Elution
125.24, 121.96, 115.57, 37.98. HR-MS: m/z 236.1422 [M+H]+, with EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 35.6
calcd for C17H18N 236.1434.
mg (68%). 1H NMR (400 MHz, CDCl3): δ 8.69 (d, J = 4.2 Hz, 1H),
2-(2-Allyl-6-methylphenyl)pyridine (3ba). Elution with EtOAc/ 7.73 (dt, J = 7.7, 1.8 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.55–7.40
petroleum ether 1/20 (v/v), colorless oil, yield 36.9 mg (88%). (m, 2H), 7.35–7.23 (m, 2H), 5.85–5.68 (m, 1H), 5.01-4.90 (m,
1H NMR (400 MHz, CDCl3): δ 8.71 (d, J = 4.7 Hz, 1H), 7.73 (dt, J 1H), 4.88–4.77 (m, 1H), 3.20-2.99 (m, 2H). 13C NMR (101 MHz,
= 7.7, 1.8 Hz, 1H), 7.30–7.20(m, 3H), 7.13 (d, J = 7.6 Hz, 2H), CDCl3): δ 156.51, 149.11, 140.30, 138.76, 136.34, 135.83,
5.87-5.72 (m, 1H), 4.94–4.87 (m, 1H), 4.84–4.76 (m, 1H), 3.12 133.06, 128.95 (q, J = 29.9 Hz), 128.37, 125.12, 125.11, 124.14
(s, 2H), 2.04 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 159.52, (q, J = 275.2 Hz), 124.03 (q, J = 5.3 Hz), 122.58, 116.41, 37.44.
149.64, 140.31, 137.80, 137.43, 136.18, 136.12, 128.15, 19F NMR (376 MHz, CDCl3): δ –57.29. HR-MS: m/z 264.0993
128.08, 126.93, 124.88, 121.86, 115.50, 37.95, 20.40. HR-MS: [M+H]+, calcd for C15H13F3N 264.0995.
m/z 210.1279 [M+H]+, calcd for C15H16N 210.1277.
2-(2-Allyl-6-fluorophenyl)pyridine (3ca). Elution
2-(2-Allyl-5-methylphenyl)pyridine (3ha). Elution with
with EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 23.0 mg
1
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 24.2mg (55%). H NMR (400 MHz, CDCl3): δ 8.68 (d, J = 4.4 Hz, 1H),
1
(57%). H NMR (400 MHz, CDCl3): δ 8.72 (d, J = 4.7 Hz, 1H), 7.71 (t, J = 7.7 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1H), 7.27-7.12 (m,
7.74 (t, J = 7.7 Hz, 1H), 7.36 (d, J = 7.7 Hz, 1H), 7.34–7.23 (m, 4H), 5.94-5.79 (m, 1H), 4.94 (d, J = 10.0 Hz, 1H), 4.88 (d, J =
2H), 7.10 (d, J = 7.7 Hz, 1H), 7.02 (t, J = 8.9 Hz, 1H), 5.86-5.70 17.1 Hz, 1H), 3.44 (d, J = 6.3 Hz, 2H), 2.36 (s, 3H). 13C NMR (101
(m, 1H), 4.92 (d, J = 10.1 Hz, 1H), 4.83 (d, J = 17.0 Hz, 1H), 3.33 MHz, CDCl3): δ 159.98, 149.27, 140.33, 137.95, 136.12, 135.91,
(d, J = 6.6 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 160.21 (d, J = 134.57, 130.60, 130.11, 129.27, 124.24, 121.76, 115.50, 37.10,
246.5 Hz), 154.01, 149.56, 140.98 (d, J = 2.4 Hz), 136.73, 21.07. HR-MS: m/z 210.1274 [M+H]+, calcd for C15H16N
136.15, 129.61 (d, J = 9.0 Hz), 128.30 (d, J = 15.5 Hz), 125.86 (d, 210.1277.
J = 1.7 Hz), 125.33 (d, J = 3.1 Hz), 122.48 , 115.98 , 113.53 (d, J 2-(2-Allyl-4,5-dimethylphenyl)pyridine (3ia). Elution with
= 22.7 Hz), 37.25 (d, J = 2.6 Hz). 19F NMR (376 MHz, CDCl3): δ – EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 17.9 mg
1
116.53. HR-MS: m/z 214.1030 [M+H]+, calcd for C14H13FN (40%). H NMR (400 MHz, CDCl3): δ 8.67 (d, J = 4.2 Hz, 1H),
214.1027.
7.69 (dt, J = 7.7, 1.8 Hz, 1H), 7.38 (d, J = 7.8 Hz, 1H), 7.24–7.16
2-(2-Allyl-4,6-difluorophenyl)pyridine (3da). Elution with (m, 2H), 7.07 (s, 1H), 5.94–5.81 (m, 1H), 4.99–4.85 (m, 2H),
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 21.1 mg 3.43 (d, J = 6.4 Hz, 2H), 2.29 (s, 3H), 2.27 (s, 3H). 13C NMR (101
1
(47%). H NMR (400 MHz, CDCl3): δ 8.72 (d, J = 4.4 Hz, 1H), MHz, CDCl3): δ 159.98, 149.27, 138.15, 138.02, 136.93, 136.05,
7.75 (t, J = 7.7 Hz, 1H), 7.34 (d, J = 7.8 Hz, 1H), 7.31–7.25 (m, 134.87, 134.57, 131.45, 131.20, 124.25, 121.55, 115.38, 37.10,
1H), 6.86 (d, J = 9.4 Hz, 1H), 6.77 (t, J = 9.1 Hz, 1H), 5.83–5.69 19.63, 19.36. HR-MS: m/z 224.1423 [M+H]+, calcd for C16H18N
(m, 1H), 4.98 (d, J = 10.0 Hz, 1H), 4.87 (d, J = 17.0 Hz, 1H), 3.31 224.1434.
(d, J = 6.6 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 162.51 (dd, J = 2-(4-Allyl-[1,1'-biphenyl]-3-yl)pyridine (3ja). Elution with
249.6, 13.2 Hz), 160.43 (dd, J = 248.8, 12.7 Hz), 153.24 , 149.69 EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 27.1 mg
1
, 142.82 (dd, J = 8.9, 3.6 Hz), 136.31 , 135.83 , 125.99 (d, J = 1.6 (50%). H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 4.8 Hz, 1H),
Hz) , 124.55 (dd, J = 15.7, 3.8 Hz), 122.65 , 116.81 , 112.32 (dd, 7.73 (dt, J = 7.7, 1.8 Hz, 1H), 7.66–7.55 (m, 4H), 7.48–7.36 (m,
J = 21.4, 3.4 Hz), 101.91 (dd, J = 26.9, 25.6 Hz), 37.26 (dd, J = 4H), 7.32 (t, J = 7.3 Hz, 1H), 7.28–7.22 (m, 1H), δ 5.97–5.84 (m,
2.6, 1.8 Hz). 19F NMR (376 MHz, CDCl3): δ –110.27 (d, J = 7.6 1H), 5.02–4.88 (m, 2H), 3.52 (d, J = 6.5 Hz, 2H). 13C NMR (101
Hz), –112.38 (d, J = 7.6 Hz). HR-MS: m/z 232.0933 [M+H]+, MHz, CDCl3): δ 159.87, 149.30, 140.89, 140.81, 139.33, 137.57,
calcd for C14H12F2N 232.0932.
136.90, 136.31, 130.65, 128.82, 128.75, 127.30, 124.28,
2-(2-Allyl-6-chlorophenyl)pyridine (3ea). Elution with EtOAc/ 121.95, 115.82, 37.24. HR-MS: m/z 272.1421 [M+H]+, calcd for
petroleum ether 1/20 (v/v), colorless oil, yield 37.2 mg (81%). C20H18N 272.1434.
1H NMR (400 MHz, CDCl3): δ 8.71 (d, J = 4.4 Hz, 1H), 7.74 (t, J = 2-(3-Allylnaphthalen-2-yl)pyridine
(3ka).
Elution
with
7.6 Hz, 1H), 7.34 (d, J = 7.9 Hz, 1H), 7.31–7.23 (m, 3H), 7.20 (d, EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 25.0 mg
1
J = 7.6 Hz, 1H), 5.86-5.67 (m, 1H), 4.93 (d, J = 10.0 Hz, 1H), 4.81 (51%). H NMR (400 MHz, CDCl3): δ 8.76–8.67 (m, 1H), 7.90-
(d, J = 17.0 Hz, 1H), 3.17 (d, J = 6.5 Hz, 2H). 13C NMR (101 MHz, 7.80 (m, 3H), 7.79–7.72 (m, 2H), 7.53–7.40 (m, 3H), 7.31-7.25
CDCl3): δ 157.08, 149.48, 140.49, 139.07, 136.44, 136.11, (m, 1H), 5.97-5.83 (m, 1H), 5.01–4.94 (m, 1H), 4.93–4.85 (m,
133.27, 129.25, 127.96, 127.39, 125.37, 122.45, 116.11, 37.93. 1H), 3.68 (d, J = 6.5 Hz, 2H). 13C NMR (101 MHz, CDCl3):
HR-MS: m/z 230.0728 [M+H]+, calcd for C14H13ClN 230.0731.
δ160.04, 149.18, 139.25, 137.46, 136.40, 135.98, 133.49,
2-(2-Allyl-6-bromophenyl)pyridine (3fa). Elution with EtOAc/ 132.12, 129.32, 128.54, 127.97, 127.36, 126.46, 125.83,
petroleum ether 1/20 (v/v), colorless oil, yield 36.4 mg (66%). 124.50, 121.95, 115.95, 37.86. HR-MS: m/z 246.1264 [M+H]+,
1H NMR (400 MHz, CDCl3): δ 8.76–8.67 (m, 1H), 7.75 (dt, J = calcd for C18H16N 246.1277.
7.7, 1.8 Hz, 1H), 7.52 (dd, J = 7.8, 1.0 Hz, 1H), 7.33–7.23 (m, 2-(2-Allylnaphthalen-1-yl)pyridine (3la). Elution with EtOAc/
3H), 7.20 (t, J = 7.7 Hz, 1H), 5.84–5.69 (m, 1H), 4.97-4.89 (m, petroleum ether 1/20 (v/v), colorless oil, yield 41.7 mg (85%).
1H), 4.86–4.76 (m, 1H), 3.23-3.07 (m, 2H). 13C NMR (101 MHz, 1H NMR (400 MHz, CDCl3): δ 8.79 (d, J = 4.7 Hz, 1H), 7.89-7.81
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(m, 2H), 7.78 (t, J = 7.6 Hz, 1H), 7.46–7.26 (m, 6H), 5.95–5.81 (71%). H NMR (400 MHz, CDCl3): δ 8.71 (d, J = 4.6 Hz, 1H),
(m, 1H), 4.96 (d, J = 10.1 Hz, 1H), 4.89 (d, J = 17.1 Hz, 1H), 7.72 (t, J = 7.9 Hz, 1H), 7.32–7.24 (m, 1H), 7.21 (d, J = 7.8 Hz,
3.38–3.22 (m, 2H). 13C NMR (101 MHz, CDCl3): δ 158.58, 1H), 7.16 (s, 2H), 5.87–5.66 (m, 2H), 4.96 (d, J = 10.1 Hz, 2H),
149.81, 137.36, 136.88, 136.15, 135.27, 132.60, 132.34, 4.83 (d, J = 17.4 Hz, 2H), 3.18–2.96 (m, 4H). 13C NMR (101 MHz,
128.50, 127.95, 127.82, 126.24, 125.91, 125.78, 125.27, CDCl3): δ 158.02, 149.71, 140.17, 138.57, 136.42, 136.15,
122.20, 115.78, 38.09. HR-MS: m/z 246.1276 [M+H]+, calcd for 133.95, 127.32, 125.28, 122.29, 116.43, 37.77. HR-MS: m/z
C18H16N 246.1277.
270.1047 [M+H]+, calcd for C17H17ClN 270.1044.
2-(2,6-Diallyl-4-methylphenyl)pyridine (3ma). Elution with 2-(2,6-Diallyl-4-bromophenyl)pyridine (3sa). Elution with
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 42.7 mg EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 40.8 mg
1
1
(86%). H NMR (400 MHz, CDCl3): δ 8.69 (d, J = 4.2 Hz, 1H), (65%). H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 4.8 Hz, 1H),
7.69 (t, J = 7.6 Hz, 1H), 7.27-9.19 (m, 2H), 6.97 (s, 2H), 5.88– 7.73 (dt, J = 7.7, 1.7 Hz, 1H), 7.31 (s, 2H), 7.30–7.24 (m, 1H),
5.68 (m, 2H), 4.90 (d, J = 10.0 Hz, 2H), 4.81 (d, J = 17.0 Hz, 2H), 7.21 (d, J = 7.7 Hz, 1H), 5.83-5.67 (m, 2H), 5.00–4.91 (m, 2H),
3.17–3.00 (m, 4H), 2.35 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 4.88–4.78 (m, 2H), 3.16–2.98 (m, 4H). 13C NMR (101 MHz,
159.20, 149.48, 137.93, 137.92, 137.53, 137.37, 135.86, CDCl3): δ 158.02, 149.71, 140.44, 139.06, 136.41, 136.15,
128.10, 125.47, 121.83, 115.47, 38.00, 21.35. HR-MS: m/z 130.25, 125.22, 122.31, 116.46, 37.72. HR-MS: m/z 314.0541
250.1592 [M+H]+, calcd for C18H20N 250.1590.
[M+H]+, calcd for C17H17BrN 314.0539.
2-(3,5-Diallyl-[1,1'-biphenyl]-4-yl)pyridine (3na). Elution with Ethyl 3,5-diallyl-4-(pyridin-2-yl)benzoate (3ta). Elution with
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 46.3 mg EtOAc/petroleum ether 1/20 (v/v), white solid, yield 49.5 mg
1
(74%). H NMR (400 MHz, CDCl3): δ 8.72 (d, J = 4.8 Hz, 1H), (81%). 1H NMR (400 MHz, CDCl3): δ 8.77–8.67 (m, 1H), 7.85 (s,
7.73 (dt, J = 7.7, 1.8 Hz, 1H), 7.66–7.59 (m, 2H), 7.44 (t, J = 7.6 2H), 7.75 (dt, J = 7.7, 1.8 Hz, 1H), 7.34–7.27 (m, 1H), 7.23 (d, J =
Hz, 2H), 7.40 (s, 2H), 7.34 (t, J = 7.3 Hz, 2H), 7.31–7.24 (m, 2H), 7.7 Hz, 1H), 5.86-5.72 (m, 2H), 5.02-4.88 (m, 2H), 4.86–4.76 (m,
5.90–5.77 (m, 2H), 4.99–4.90 (m, 2H), 4.89–4.81 (m, 2H), 3.29– 2H), 4.39 (q, J = 7.1 Hz, 2H), 3.26–3.05 (m, 4H), 1.41 (t, J = 7.1
3.08 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 158.88, 149.60, Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 166.66, 158.11, 149.59,
141.21, 139.16, 138.61, 137.27, 135.99, 128.80, 127.38, 144.39, 138.61, 136.65, 136.10, 130.30, 128.61, 124.94,
127.32, 126.32, 125.36, 122.05, 115.84, 38.16. HR-MS: m/z 122.37, 116.15, 61.08, 37.87, 14.44. HR-MS: m/z 308.1639
312.1749 [M+H]+, calcd for C23H22N 312.1747.
[M+H]+, calcd for C20H22NO2 308.1645.
2-(2,6-Diallyl-4-methoxyphenyl)pyridine (3oa). Elution with 3,5-Diallyl-4-(pyridin-2-yl)benzoic acid (3ua). Elution with
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 44 mg EtOAc/petroleum ether 1/3 (v/v), white solid, yield 39.6 mg
1
(83%). H NMR (400 MHz, CDCl3): δ 8.61 (d, J = 4.4 Hz, 1H), (71%). 1H NMR (400 MHz, DMSO-d6): δ 13.04 (b, 1H), 8.69 (d, J
7.61 (t, J = 7.6 Hz, 1H), 7.20–7.10 (m, 2H), 6.83 (s, 2H), 5.78– = 4.3 Hz, 1H), 7.88 (dt, J = 7.7, 1.7 Hz, 1H), 7.75 (s, 2H), 7.45–
5.62 (m, 2H), 4.84 (d, J = 10.0 Hz, 2H), 4.74 (d, J = 17.0 Hz, 2H), 7.38 (m, 1H), 7.33 (d, J = 7.7 Hz, 1H), 5.80–5.66 (m, 2H), 4.96-
3.73 (s, 3H), 3.11–2.92 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 4.88 (m, 2H), 4.87–4.78 (m, 2H), 3.09 (s, 4H). 13C NMR (101
159.30, 158.95, 149.46, 139.65, 137.12, 135.88, 133.02, MHz, DMSO-d6): δ 167.18, 157.24, 149.41, 144.22, 138.25,
125.73, 121.80, 115.77, 112.68, 55.26, 38.16. HR-MS: m/z 136.66, 136.40, 130.37, 128.04, 124.74, 122.65, 116.20, 37.21.
266.1541 [M+H]+, calcd for C18H20NO 266.1539.
HR-MS: m/z 280.1328 [M+H]+, calcd for C18H18NO2 280.1332.
3,5-Diallyl-4-(pyridin-2-yl)phenol (3pa). Elution with EtOAc/ 2-(2,6-Diallyl-4-(trifluoromethyl)phenyl)pyridine (3va). Elution
petroleum ether 1/3 (v/v), white solid, yield 36.3 mg (72%). 1H with EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 41.8
NMR (400 MHz, CDCl3): δ 9.96-9.23 (b, 1H), 8.67 (d, J = 3.8 Hz, mg (69%). 1H NMR (400 MHz, CDCl3): δ 8.72 (d, J = 4.8 Hz, 1H),
1H), 7.75 (t, J = 7.3 Hz, 1H), 7.36–7.22 (m, 2H), 6.39 (s, 2H), 7.76 (dt, J = 7.7, 1.7 Hz, 1H), 7.43 (s, 2H), 7.34–7.28 (m, 1H),
5.75–5.60 (m, 2H), 4.83 (d, J = 9.8 Hz, 2H), 4.71 (d, J = 17.0 Hz, 7.23 (d, J = 7.7 Hz, 1H), 5.85–5.70 (m, 2H), 4.98 (dd, J = 10.0,
2H), 3.08–2.84 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 158.94, 1.1 Hz, 2H), 4.84 (dd, J = 17.0, 1.5 Hz, 2H), 3.25–3.05 (m, 4H).
156.93, 148.44, 139.27, 137.15, 136.77, 130.95, 126.59, 13C NMR (101 MHz, CDCl3): δ 157.77, 149.81, 143.47, 139.31,
122.28, 115.55, 115.465, 38.01. HR-MS: m/z 252.1377 [M+H]+, 136.24, 130.50 (q, J = 32.1 Hz), 124.92, 124.29 (q, J = 273.4 Hz),
calcd for C17H18NO 252.1383.
124.18 (q, J = 3.7 Hz), 122.52, 116.63, 37.88. 19F NMR (376
2-(2,6-Diallyl-4-fluorophenyl)pyridine (3qa). Elution with MHz, CDCl3): δ –62.55. HR-MS: m/z 304.1289 [M+H]+, calcd for
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 33.1 mg C18H17F3N 304.1308.
1
(65%). H NMR (400 MHz, CDCl3): δ 8.71 (d, J = 4.4 Hz, 1H), 2-(2,6-Diallyl-4-nitrophenyl)pyridine (3wa). Elution with
7.73 (dt, J = 7.7, 1.8 Hz, 1H), 7.31–7.25 (m, 1H), 7.22 (d, J = 8.0 EtOAc/petroleum ether 1/10 (v/v), colorless oil, yield 25.1 mg
Hz, 1H), 6.88 (d, J = 9.6 Hz, 2H), 5.85–5.69 (m, 2H), 4.96 (dd, J = (45%). 1H NMR (400 MHz, CDCl3): δ 8.79–8.71 (m, 1H), 8.05 (s,
10.4, 1.6 Hz, 2H), 4.84 (dd, J = 17.2, 1.6 Hz, 2H), 3.20–2.97 (m, 2H), 7.81 (dt, J = 7.7, 1.7 Hz, 1H), 7.43–7.33 (m, 1H), 7.26 (d, J =
4H). 13C NMR (101 MHz, CDCl3) δ 162.57 (d, J = 246.7 Hz), 7.8 Hz, 1H), 5.88-5.72 (m, 2H), 5.10–4.98 (m, 2H), 4.97–4.79
158.30, 149.70, 140.74 (d, J = 7.7 Hz), 136.49, 136.15, 136.12, (m, 2H), 3.29–3.08 (m, 4H). 13C NMR (101 MHz, CDCl3): δ
125.49, 122.20, 116.38, 113.98 (d, J = 21.4 Hz), 37.92 (d, J = 1.6 156.90, 149.90, 147.77, 146.18, 140.49, 136.45, 135.52,
Hz). 19F NMR (376 MHz, CDCl3): δ –114.36. HR-MS: m/z 124.65, 122.86, 122.21, 117.24, 37.77. HR-MS: m/z 281.1285
254.1341 [M+H]+, calcd for C17H17FN 254.1340.
[M+H]+, calcd for C17H17N2O2 281.1285.
2-(2,6-Diallyl-4-chlorophenyl)pyridine (3ra). Elution with 2-(2,6-Diallyl-3-methoxyphenyl)pyridine (3xa). Elution with
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 38.3 mg EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 42.3 mg
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(80%). 1H NMR (400 MHz, CDCl3): δ 8.72-8.66 (m, 1H), 7.69 (dt,
J = 7.7, 1.8 Hz, 1H), 7.29–7.18 (m, 2H), 7.12 (d, J = 8.4 Hz, 1H),
6.89 (d, J = 8.5 Hz, 1H), 5.86–5.70 (m, 2H), 4.92–4.85 (m, 1H),
4.84–4.74 (m, 2H), 4.69–4.60 (m, 1H), 3.83 (s, 3H), 3.28–3.18
(m, 1H), 3.11–2.94 (m, 3H). 13C NMR (101 MHz, CDCl3): δ
158.93, 156.10, 149.33, 141.41, 137.80, 136.95, 135.72,
130.15, 128.01, 126.55, 125.28, 121.97, 115.18, 114.40,
110.62, 55.83, 37.43, 31.81. HR-MS: m/z 266.1534 [M+H]+,
calcd for C18H20NO 266.1539.
Acknowledgements
Financial support from the National Natural Science
Foundation of China (Grant No. 21372212) and the National
Basic Research Program of China (Grant No. 2015CB856600) is
greatly acknowledged.
Notes and references
1
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1
(82%). H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 4.4 Hz, 1H),
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1,
7.72 (t, J = 7.6 Hz, 1H), 7.32–7.25 (m, 1H), 7.23 (d, J = 7.8 Hz,
1H), 7.16–7.09 (m, 1H), 7.04 (t, J = 8.9 Hz, 1H), 5.85–5.67 (m,
2H), 4.91 (d, J = 10.3 Hz, 1H), 4.87 (d, J = 10.1 Hz, 1H), 4.79 (d, J
= 17.0 Hz, 1H), 4.72 (d, J = 17.1 Hz, 1H), 3.31–3.16 (m, 1H),
3.15-2.96 (m, 3H). 13C NMR (101 MHz, CDCl3): δ 159.87 (d, J =
244.2 Hz), 157.80 (d, J = 2.8 Hz), 149.48, 141.90 (d, J = 4.2 Hz),
137.12 , 135.93 , 135.80 , 133.78 (d, J = 3.5 Hz), 128.66 (d, J =
8.6 Hz), 125.17 (d, J=16.2), 125.14 , 122.30 , 115.70 , 115.24 ,
115.00 (d, J = 22.5 Hz), 37.40 , 30.88 (d, J = 3.1 Hz). 19F NMR
(376 MHz, CDCl3): δ –120.17. HR-MS: m/z 254.1332 [M+H]+,
calcd for C17H17FN 254.1340.
8
7
3
4
2-(2,6-Diallyl-3-chlorophenyl)pyridine (3za). Elution with
EtOAc/petroleum ether 1/20 (v/v), colorless oil, yield 31.3 mg
1
(58%). H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 4.8 Hz, 1H),
7.72 (dt, J = 7.7, 1.8 Hz, 1H), 7.37 (d, J = 8.3 Hz, 1H), 7.31–7.25
(m, 1H), 7.22 (d, J = 7.8 Hz, 1H), 7.11 (d, J = 8.3 Hz, 1H), 5.84–
5.68 (m, 2H), 4.96–4.87 (m, 2H), 4.84-4.76 (m, 1H), 4.73–4.63
(m, 1H), 3.39–3.29 (m, 1H), 3.19-3.11 (m, 1H), 3.11–2.94 (m,
2H). 13C NMR (101 MHz, CDCl3): δ158.29, 149.53, 142.15,
137.08, 136.75, 135.98, 135.44, 135.11, 132.83, 129.41,
128.62, 125.14, 122.37, 116.03, 115.67, 37.66, 35.32. HR-MS:
m/z 270.1031 [M+H]+, calcd for C17H17ClN 270.1044.
5
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petroleum ether 1/20 (v/v), colorless oil, yield 31.0 mg (69%).
1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 1.5 Hz, 1H), 7.44 (d, J =
2.2 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.19 (d, J = 7.7 Hz, 2H), 6.42
(t, J = 2.0 Hz, 1H), 5.89–5.72 (m, 2H), 5.03–4.94 (m, 2H), 4.93–
4.85 (m, 2H), 3.02 (d, J = 14.4 Hz, 4H). 13C NMR (101 MHz,
CDCl3): δ 140.20, 138.57, 138.45, 136.76, 131.91, 129.45,
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6
7
8
S. E. Korkis, D. J. Burns, and H. W. Lam, J. Am. Chem. Soc.,
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2-(2,6-Diallylphenyl)pyrimidine (5). Elution with EtOAc/
petroleum ether 1/20 (v/v), colorless oil, yield 36.8 mg (78%).
1H NMR (400 MHz, CDCl3): δ 8.84 (d, J = 4.9 Hz, 2H), 7.34–7.28
(m, 1H), 7.26 (t, J = 5.0 Hz, 1H), 7.17 (d, J = 7.6 Hz, 2H), 5.83–
5.71 (m, 2H), 4.85 (dq, J = 10.0, 2.0 Hz, 2H), 4.77 (dq, J = 16.8,
2.0 Hz, 2H), 3.21 (d, J = 6.8 Hz, 4H). 13C NMR (101 MHz, CDCl3):
δ 167.92, 156.93, 138.65, 137.93, 137.00, 128.94, 127.63,
119.11, 115.51, 38.04. HR-MS: m/z 237.1389 [M+H]+, calcd for
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Conflicts of interest
There are no conflicts to declare.
Zhang, Z. J. Liu, and H. M. Huang, RSC Adv., 2014, 4, 64235;
8 | J. Name., 2012, 00, 1-3
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Graphical abstract
Ruthenium-Catalyzed C-H Allylation of Arenes with Allylic Amines
Rui Yan and Zhong-Xia Wang*
The Ru-catalyzed pyridyl-directed C-H allylation of arenes with allylic amines was carried
out in the presence of 5 mol % of [Ru(p-cymene)Cl2]2 and 0.5 equiv. of AgOAc in
CF3CH2OH.