Friedel-crafts-type allylation of nitrogen-containing aromatic compounds with allylic alcohols catalyzed by a [Mo3S4Pd(η 3-allyl)] cluster

Article abstract of DOI:10.1021/jo2024812

With the direct use of allylic alcohols as allylating agents, the Friedel-Crafts-type allylic alkylation of nitrogen-containing aromatic compounds catalyzed by a [Mo₃S₄Pd(η³-allyl)] cluster is achieved. With a 3 mol % catalyst loading in acetonitrile at reflux or 60 °C, a variety of N,N-dialkylanilines and indoles reacted smoothly with allylic alcohols to afford the Friedel-Crafts-type allylation products in good to excellent yields with high levels of regioselectivity.

Full text of DOI:10.1021/jo2024812

Note
pubs.acs.org/joc
Friedel−Crafts-Type Allylation of Nitrogen-Containing Aromatic
Compounds with Allylic Alcohols Catalyzed by a [Mo3S4Pd(η3-allyl)]
Cluster
Yinsong Tao, Baomin Wang, Jinfeng Zhao, Yuming Song, Lihong Qu, and Jingping Qu*
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and
Biological Science and Technology, Dalian University of Technology, Dalian 116024, P. R. China
S
* Supporting Information
ABSTRACT: With the direct use of allylic alcohols as allylating agents, the Friedel−Crafts-type allylic alkylation of nitrogen-
containing aromatic compounds catalyzed by a [Mo3S4Pd(η3-allyl)] cluster is achieved. With a 3 mol % catalyst loading in
acetonitrile at reflux or 60 °C, a variety of N,N-dialkylanilines and indoles reacted smoothly with allylic alcohols to afford the
Friedel−Crafts-type allylation products in good to excellent yields with high levels of regioselectivity.
reen chemistry has been attracting increasing interest
from both academic and industrial communities owing
latter one is more favorable in terms of the efficiency of the
promoter. In the context of transition-metal catalysis for Friedel−
Crafts-allylating with allylic alcohols, ruthenium and palladium
complexes are most studied, as exemplified by the elegant research
work from the groups of Hidai,5 Pregosin,6 Tamaru,7 Trost,8 and
Breit.9 Given the salient advantages associated with the direct use
of allylic alcohols as allylating agent, the development of more
efficient and practical catalyst system for this process is still in high
demand.
As a part of our ongoing project aimed at developing environ-
mentally benign chemical transformations, we have recently shown
that the novel cubane-type sulfido cluster incorporating Mo and
Pd, [(Cp*Mo)3(μ3-S)4Pd(η3-allyl)][PF6]2, (Cp* = η5-C5Me5) (1)
could efficiently catalyze the allylation of amines and active
methylene compounds in excellent regioselectivity with the direct
use of allylic alcohols as allylating agent.10 Note that Hidai and co-
workers have first demonstrated the unique catalytic activities of
cubane-type Mo3MS4 (M = Pd, Ni) clusters for organic syn-
thesis.11 As a logical extension of our previous work, we
further find that the Friedel−Crafts-type allylation of N,N-
dialkylaniline and indole could occur smoothly under the
catalysis of the Mo, Pd-based cubane-type sulfido cluster. We
wish to present herein the experimental results.
G
to its great potential on lowering the environmental pressure
brought about by pollutive chemical processes.1 Among the
various criteria used to define a green process, one significant facet
is to minimize or, ideally, to completely avoid the forma-
tion of waste byproducts. To this end, replacing the reactants that
produce undesired byproducts by less or nonwaste-producing
ones provides an excellent solution. Consequently, a number of
environmentally benign chemical processes have been developed
on the basis of this strategy. The Friedel−Crafts-type allylic alkyla-
tion of aromatic and heteroaromatic compounds represents a typical
member among the category of allylatively alkylating transforma-
tions and constitutes one of the most important tools for the
construction of the carbon−carbon bond.2 Most frequently, allylic
compounds such as allyl acetate, carbonate, and halide are employed
as allylic substrates in the allylic alkylation reactions. However,
the use of these substrates would inevitably produce waste bypro-
ducts in stoichiometric amount. Alternatively, from a viewpoint of
economy and environment, the ideal substrate for allylic alkylation
should be allylic alcohols since water is the only byproduct in such
case.
Although the studies with the direct use of allylic alcohols as
allylating agents are limited because of the poor leaving-group
character of the hydroxyl function, reports toward this project
are increasing.3 In the specific case of Friedel−Crafts-type allylic
alkylation of aromatic and heteroaromatic compounds with allylic
alcohols as substrate, two kinds of activator have been reported,
stoichiometric or catalytic Brønsted/Lewis acid and transition-
metal complex in catalytic amounts, respectively.4 In contrast, the
The first experiments were focused on the identification of the
optimal reaction conditions. Thus, the Friedel−Crafts reaction of
N,N-dimethylaniline (3a) with cinnamyl alcohol (2a) was chosen
as the model reaction. Subjection of the two reactants to the
Received: December 2, 2011
Published: February 16, 2012
© 2012 American Chemical Society
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Note
catalysis of 3 mol % of various promoters in acetonitrile at reflux
was evaluated so as to identify the best catalyst, and the results are
compiled in Table 1.
(3e) gave a low product yield of 35%, the o-methyl-substituted
one (3f) is completely unreactive. This fact may be due to a
combination of the steric and electronic effects. Interestingly, m-
bromo-N,N-dimethylaniline (3h) underwent the reaction
smoothly, affording the product in 91% yield, which can be
further manipulated by coupling reactions. The substrate scope in
terms of allylic alcohol was also examined, with 2b, 2c, and 2d
reacting smoothly with 3a to furnish the corresponding product in
high yield, respectively. The fact that allylic alcohols 2a and 2b
gave the same allylated product indicates that a common π-allyl-
palladium intermediate exists in this process. A final remark con-
cerns the allylation of secondary amine N-methyaniline (3i), and it
was found both nitrogen and p-carbon were allylated in such cases.
The indole moiety is a significant motif in a vast number of
bioactive natural alkaloids and synthetic drugs. As such, the
synthesis and functionalization of indole has been drawn much
attention from synthetic and pharmaceutical chemists.16 After
the allylation of N,N-dialkylaniline was successfully investigated,
we focused our attention on the allylic alkylation of indoles.
Very recently, Breit and co-workers documented the first
palladium catalyst system with self-assembling ligands based on
complementary hydrogen-bonding, which allowed the allylation
of indoles with the direct use of allylic alcohols as allylat-
ing agents.9 Comparably, when indole (5a) was treated with
cinnamyl alcohol (2a) over our cubane-type palladium catalyst,
to our delight, the desired allylation product was obtained in
83% yield (Table 3, entry 1). Some other representative sub-
stituted indoles, such as 5-methoxyindole (5b), 5-bromoindole
(5c), and 2-methylindole (5d), could serve as reactive sub-
strates as well (entries 2−4). In addition, N-methyl- and N-
phenylindole (5e, 5f) were also allylated smoothly by cinnamyl
alcohol (2a) (entries 5 and 6). The allylic alcohols 2b and 2a
afforded the same product when treated with indole (entry 7),
again indicating a common π-allylpalladium intermediate in-
volved in this process.
a
Table 1. Evaluation of Reaction Conditions
b
entry
cat.
yield (%)
1
2
p-TsOH·H2O
HPF6 (60%)
AuCl3
nr
nr
nr
nr
nr
nr
nr
nr
38
87
nr
nr
3
4
FeCl3
5
ZnCl2
6
PdCl2
[(η3-allyl)PdCl]2
7
8
Pd(PPh3)4
9
[(Cp*Mo)3(μ3-S)4Pd(dba)][PF6]
10
11
12
[(Cp*Mo)3(μ3-S)4Pd(η3-allyl)][PF6]2 (1)
[{(Cp*Mo)3(μ3-S)4Ni}2(cod)][PF6]2
[(Cp*Mo)3(μ3-S)4RuH2(PPh3)][PF6]
a
Reaction conditions: N,N-dimethylaniline (0.4 mmol), cinnamyl
alcohol (0.4 mmol), cat. (0.012 mmol), MeCN (1 mL), reflux, 6 h.
b
Isolated yield.
The Brønsted acids, p-TsOH·H2O and HPF6, failed to
catalyze this reaction probably due to the scavenging of the
proton by the basic N,N-dimethylaniline (entries 1−2).
12
13
Notably, no allylation was observed when AuCl3 or FeCl3
was used as catalyst (entries 3 and 4), which in contrast showed
high efficiency on the allylic alkylation of phenols and benzyla-
tion of aromatic compounds, respectively. ZnCl2, a typical Lewis
acid, did not work for this process either (entry 5). Despite the
sporadic reports wherein palladium complexes exhibited excellent
performance in the allylation of aromatic and heteroaromatic
compounds with allylic alcohols, simple palladium catalysts, such
as PdCl2, [(η3-allyl)PdCl]2, and Pd(PPh3)4, could not promote the
model reaction (entries 6−8). When a cubane-type sulfido cluster
involving Pd in combination with dba as a ligand14 was examined,
however, a 38% product yield was obtained (entry 9). Gratifyingly,
further investigation showed that the cubane-type sulfido cluster
[(Cp*Mo)3(μ3-S)4Pd(η3-allyl)][PF6]2, (Cp* = η5-C5Me5) (1)
could catalyze the allylation reaction smoothly in 87% product
yield (entry 10). Other cubane-type sulfido clusters involving Ru14
or Ni15 showed no catalytic activity toward this transformation
(entries 11 and 12).
Although no experimental details were provided to probe the
insights into the reaction mechanism, we surmise that the pathway
of the current transformation resembles that of the allylation of
active methylene compounds just reported by our group.10b
In summary, we have discovered that the novel cubane-
type sulfido cluster [(Cp*Mo)3(μ3-S)4Pd(η3-allyl)][PF6]2 is
a valuable catalyst with unique catalytic activities, which
allows the highly efficient Friedel−Crafts-type allylation of
nitrogen-containing aromatic compounds including N,N-
dialkylaniline and indole with the direct use of allylic alco-
hols as allylating agents. We anticipate that this process
would find use in the synthesis of natural alkaloids.
With the optimal reaction conditions in hand, we next investiga-
ted the substrate scope of the Friedel−Crafts-type allylation with
allylic alcohols. Compared to alkylbenzenes, phenols, and anisoles,
N,N-dialkylanilines are rarely employed as substrate in the transi-
tion metal or Lewis acid catalyzed Friedel−Crafts-type allylation
with allylic alcohols as the allylating agent. It is worthy of note that
our catalyst system is especially effective for allylating N,N-dialkyl-
aniline compounds. From Table 2, we can see that various N,N-
dialkylanilines could be allylated smoothly under the standard
reaction conditions (entries 1−4, 6, and 7). Notably, the substitu-
tion manner of methyl group on the benzene ring exhibited
marked influence on the reactivity of the aniline substrate, as can
be seen in the cases of 3e, 3f, and 3g. The m-methyl-substituted
N,N-dimethylaniline (3g) is most reactive, affording the product in
84% yield. While the p-methyl-substituted N,N-dimethylaniline
EXPERIMENTAL SECTION
■
All manipulations were carried out under an argon atmosphere using
conventional Schlenk techniques. All commercially available reagents
were used as received unless otherwise noted. All solvents were dried
and distilled by standard methods before use. The cubane-type cata-
lysts, [(Cp*Mo)3(μ3-S)4Pd(dba)][PF6],14 [(Cp*Mo)3(μ3-S)4-
RuH2(PPh3)][PF6],14 [{(Cp*Mo)3(μ3-S)4Ni}2(cod)][PF6]2,15 and
[(Cp*Mo)3(μ3-S)4Pd(η3-allyl)][PF6]2 (1),10b were synthesized accord-
ing to literature procedures. NMR spectra were recorded on a
400 MHz spectrometer. Chemical shifts were reported in ppm relative
to TMS.
General Reaction Procedure for the Friedel−Crafts-type
Allylation of N,N-Dialkylated Anilines and Indoles. [(Cp*Mo)3-
(μ3-S4)Pd(η3-allyl)][PF6]2 (1) (0.012 mmol) was added to a 25 mL
Schlenk tube under argon, and then MeCN (1 mL), aniline or indole
compounds (0.4 mmol), and allylic alcohol (0.4 mmol) were added
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Note
a
Table 2. Friedel−Crafts-Type Reaction of Anilines with Allylic Alcohols Catalyzed by 1
a
b
c
Reaction conditions: 1 (0.012 mmol), 2 (0.4 mmol), 3 (0.4 mmol), MeCN (1 mL), reflux. Isolated yield. 1 (0.02 mmol), 2a (0.8 mmol),
3i (0.4 mmol).
stepwise. The tube was sealed and heated to the appointed
temperature. The reaction was monitored by TLC. The products
were obtained by column chromatography on silica gel (eluent:
petroleum ether/EtOAc = 20/1).
N,N-Dimethyl-4-cinnamylaniline, 4aa. Following the general
procedure, 4aa was obtained as a light yellow oil: 1H NMR (400 MHz,
CDCl3) δ 2.91(s, 6 H), 3.45(d, J = 6.4 Hz, 2 H,), 6.34 (dt, J = 15.9, 6.4
Hz, 1 H), 6.43 (d, J = 15.9 Hz, 1 H), 6.71(d, J = 8.6 Hz, 2 H), 7.11(d,
J = 8.6 Hz, 2 H), 7.18 (m, 1 H), 7.27 (m, 2 H), 7.34 (d, J = 7.2 Hz, 2
H); 13C NMR (100 MHz, CDCl3) δ 38.4, 40.9, 113.1, 126.1, 126.9,
128.3, 128.5, 129.3, 130.2, 130.4, 137.8, 149.3.
38.5, 51.0, 112.1, 126.18, 126.53, 126.95, 128.5, 129.5, 130.29, 130.5,
137.9, 146.8; HRMS (APCI, positive) calcd for C23H32N ([M + H]+)
322.2535, found 322.2525.
(E)-1-(4-Cinnamylphenyl)piperidine, 4ac. Following the general
procedure, 4ac was obtained as a light yellow oil: 1H NMR (400 MHz,
CDCl3) δ 1.69 (m, 4 H), 1.54 (m, 2 H), 3.10 (t, J = 5.4 Hz, 4 H), 3.45
(d, J = 6.4 Hz, 2 H), 6.33 (dt, J = 15.8, 6.4 Hz, 1 H), 6.42 (d, J = 15.8
Hz, 1 H), 6.89 (d, J = 8.5 Hz, 2 H), 7.11 (d, J = 8.5 Hz, 2 H), 7.17 (m,
1 H), 7.27 (m, 2 H), 7.34 (d, J = 7.4 Hz, 2 H); 13C NMR (100 MHz,
CDCl3) δ 24.4, 26.0, 38.5, 51.1, 116.9, 126.2, 127.0, 128.5, 129.3,
129.97, 130.6, 130.85, 137.7, 150.9; HRMS (APCI, positive) calcd for
C20H24N ([M + H]+) 278.1909, found 278.1917.
N,N-Dibutyl-4-cinnamylaniline, 4ab. Following the general
1
procedure, 4ab was obtained as a light yellow oil: H NMR (400
N-Benzyl-4-cinnamyl-N-methylaniline, 4ad. Following the
1
MHz, CDCl3) δ 0.94 (t, J = 7.2 Hz, 6 H), 1.29−1.36 (m, 4 H), 1.51−
1.58 (m, 4 H), 3.23 (t, J = 7.6 Hz, 4 H), 3.43 (d, J = 6.5 Hz, 2 H), 6.34
(dt, J = 15.9, 6.5 Hz, 1 H), 6.43 (d, J = 15.9 Hz, 1 H), 6.60 (d, J = 8.6
Hz, 2 H), 7.07 (d, J = 8.6 Hz, 2 H), 7.27 (m, 2 H), 7.17 (m, 1 H), 7.35
(d, J = 7.4 Hz, 2 H); 13C NMR (100 MHz, CDCl3) δ 14.2, 20.5, 29.5,
general procedure, 4ad was obtained as a light yellow oil: H NMR
(400 MHz, CDCl3) δ 2.99 (s, 3 H), 3.45 (d, J = 4.0 Hz, 2 H), 4.50 (s,
2 H), 6.30−6.44 (m, 2 H), 6.69−7.36 (m, 14 H); 13C NMR (100
MHz, CDCl3) δ 38.41, 38.65, 56.9, 112.7, 126.1, 126.84, 126.87,
126.93, 128.0, 128.48, 128.57, 129.4, 130.23, 130.37, 137.8, 139.2,
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Note
131.6, 133.4, 137.6, 144.3, 149.3; HRMS (APCI, positive) calcd for
C23H24N ([M + H]+) 314.1909, found 314.1905.
Table 3. Friedel−Crafts-type Reaction of Indoles with Allylic
a
Alcohols Catalyzed by 1
(E)-N,N-Dimethyl-4-(4-phenylbut-3-en-2-yl)aniline, 4da. Fol-
lowing the general procedure, 4da was obtained as a light yellow oil:
1H NMR (400 MHz, CDCl3) δ 1.43 (d, J = 7.0 Hz, 3 H), 2.91 (s, 6 H),
3.56 (m, 1 H), 6.33 (m, 2 H), 6.72 (d, J = 8.7 Hz, 2 H), 7.14−7.20 (m,
3 H), 7.27 (m, 2 H), 7.35 (d, J = 7.3 Hz, 2 H); 13C NMR (100 MHz,
CDCl3) δ 21.3, 41.0, 41.6, 113.1, 126.2, 126.9, 127.94, 127.95, 128.5,
133.8, 136.1, 137.9, 149.3; HRMS (APCI, positive) calcd for C18H22N
([M + H]+) 252.1752, found 252.1759.
N,4-Dicinnamyl-N-methylaniline, 4ai. Following the general
procedure, 4ai was obtained as a light yellow oil: 1H NMR (400 MHz,
CDCl3) δ 2.95 (s, 3 H), 3.46 (d, J = 8 Hz, 2 H), 4.06 (d, J = 8 Hz,
2 H), 6.21−6.54 (m, 4 H), 6.75 (d, J = 8 Hz, 2 H), 7.11 (d, J = 8 Hz,
2 H), 7.17−7.27 (m, 10 H); 13C NMR (100 MHz, CDCl3) δ 38.4, 38.6,
55.4, 113.2, 126.0, 126.3, 126.5, 127.1, 127.6, 128.3, 128.63, 128.70, 129.6,
130.37, 130.53, 131.5, 137.1, 137.9, 148.3; HRMS (APCI, positive) calcd
for C25H26N ([M + H]+) 340.2065, found 340.2068.
3-Cinnamylindole, 6aa. Following the general procedure, 6aa was
obtained as a white solid: mp 89−91 °C; 1H NMR (400 MHz, CDCl3)
δ 3.69 (d, J = 8.0 Hz, 2 H), 6.43−6.52 (m, 2 H), 7.04−7.65 (m, 10 H),
7.98 (s, 1 H); 13C NMR (100 MHz, CDCl3) δ 29.0, 111.2, 114.6, 119.2,
119.4, 121.9, 122.1, 126.2, 127.0, 127.5, 128.6, 129.4, 130.5, 136.5, 137.8.
3-Cinnamyl-5-methoxyindole, 6ab. Following the general
procedure, 6ab was obtained as a light yellow solid: mp 80.5−82.5
°C; 1H NMR (400 MHz, CDCl3) δ 3.64 (d, J = 8 Hz, 2 H), 3.83 (s, 3
H), 6.42−6.55 (m, 2 H), 6.84−7.36 (m, 9 H), 7.90 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ 29.0, 55.9, 101.0, 111.9, 112.2, 114.2, 122.7,
126.1, 127.0, 127.9, 128.5, 129.2, 130.5, 131.6, 137.7, 153.9.
3-Cinnamyl-5-bromoindole, 6ac. Following the general proce-
dure, 6ac was obtained as a light yellow solid: mp 99−103 °C; H
NMR (400 MHz, CDCl3) δ 3.61 (d, J = 8 Hz, 2 H), 6.37−6.52 (m, 2 H),
7.0−7.74 (m, 9 H), 7.96 (s, 1 H); 13C NMR (100 MHz, CDCl3) δ 28.7,
112.59, 112.67, 114.4, 121.7, 123.1, 124.9, 126.2, 127.1, 128.55, 128.72,
129.3, 130.8, 135.0, 137.6.
1
a
Reaction conditions: 1 (0.012 mmol), 2 (0.4 mmol), 5 (0.4 mmol),
b
MeCN (1 mL), 60 °C. Isolated yield.
148.4; HRMS (APCI, positive) calcd for C23H24N ([M + H]+)
314.1909, found 314.1904.
2-Methyl-3-cinnamylindole, 6ad. Following the general proce-
2-Cinnamyl-4-methyl-N,N-dimethylaniline, 4ae. Following the
1
1
dure, 6ad was obtained as a light yellow solid: mp 69−71 °C; H
general procedure, 4ae was obtained as a light yellow oil: H NMR
NMR (400 MHz, CDCl3) δ 2.38 (s, 3 H), 3.61 (d, J = 4 Hz, 2 H),
6.33−6.45 (m, 2 H), 7.04−7.54 (m, 9 H), 7.75 (s, 1 H); 13C NMR
(100 MHz, CDCl3) δ 11.7, 27.8, 109.4, 110.2, 118.3, 119.2, 121.0,
126.1, 126.8, 128.4, 128.8, 129.60,129.79, 131.4, 135.3, 137.8.
3-Cinnamyl-N-methylindole, 6ae. Following the general proce-
(400 MHz, CDCl3) δ 2.27 (s, 3 H), 2.68 (s, 6 H), 3.63 (d, J = 6.4 Hz,
2 H), 6.37 (dt, J = 15.8, 6.4 Hz, 1 H), 6.48 (d, J = 15.8 Hz, 1 H), 7.02−
7.05 (m, 3 H), 7.20 (m, 1 H), 7.29 (m, 2 H), 7.37 (d, J = 7.3 Hz, 2 H);
13C NMR (100 MHz, CDCl3) δ 20.8, 34.0, 45.3, 119.3, 126.1, 126.9,
127.5, 128.5, 130.0, 130.85, 130.90, 132.7, 134.6, 137.8, 150.2; HRMS
(APCI, positive) calcd for C18H22N ([M + H]+) 252.1752, found
252.1754.
1
dure, 6ae was obtained as a light yellow oil: H NMR (400 MHz,
CDCl3) δ 3.64 (d, J = 8 Hz, 2 H), 3.67 (s, 3 H), 6.39−6.53 (m, 2 H),
6.83−7.32 (m, 10 H); 13C NMR (100 MHz, CDCl3) δ 29.0, 32.7,
109.3, 113.1, 118.9, 119.3, 121.7, 126.2, 126.8, 127.1, 128.0, 128.6,
129.6, 130.4, 137.3, 137.9.
3-Methyl-4-cinnamyl-N,N-dimethylaniline, 4ag. Following the
1
general procedure, 4ag was obtained as a light yellow oil: H NMR
(400 MHz, CDCl3) δ 2.30 (s, 3 H), 2.91 (s, 6 H), 3.45(d, J = 4.7 Hz,
2 H,), 6.33 (m, 2 H), 6.58 (m, 2 H), 7.06(d, J = 8.0 Hz, 1 H), 7.17 (m,
1 H), 7.26 (m, 2 H), 7.33 (d, J = 7.3 Hz, 2 H); 13C NMR (100 MHz,
CDCl3) δ 20.2, 36.2, 41.1, 110.9, 115.1, 126.2, 126.7, 127.0, 128.6,
129.77, 130.14, 130.36, 137.2, 137.9, 149.7; HRMS (APCI, positive)
calcd for C18H22N ([M + H]+) 252.1752, found 252.1747.
3-Cinnamyl-N-phenylindole, 6af. Following the general proce-
1
dure, 6af was obtained as a light yellow solid: mp 57.5−59.5 °C; H
NMR (400 MHz, CDCl3) δ 3.74 (d, J = 4 Hz, 2 H), 6.46−6.61 (m, 2
H), 7.08−7.50 (m, 15H); 13C NMR (100 MHz, CDCl3) δ 28.9, 110.6,
115.7, 119.5, 120.0, 122.5, 124.1, 125.7, 126.14, 126.16, 127.1, 128.5,
128.90, 128.93, 129.6, 130.8, 136.2, 137.7, 139.9; HRMS (APCI,
positive) calcd for C23H20N ([M + H]+) 310.1596, found 310.1618.
3-Bromo-4-cinnamyl-N,N-dimethylaniline, 4ah. Following the
1
general procedure, 4ah was obtained as a light yellow oil: H NMR
(400 MHz, CDCl3) δ 2.91 (s, 6 H), 3.56 (d, J = 6.2 Hz, 2 H), 6.32 (dt,
J = 15.9, 6.2 Hz, 1 H), 6.41 (d, J = 15.9 Hz, 1 H), 6.63 (dd, J = 8.5, 2.4
Hz, 1 H), 6.91 (d, J = 2.4 Hz, 1 H), 7.10 (d, J = 8.5 Hz, 1 H), 7.18 (m,
1 H), 7.27 (m, 2 H), 7.35 (d, J = 7.5 Hz, 2 H); 13C NMR (100 MHz,
CDCl3) δ 150.4, 137.8, 131.1, 130.8, 128.74, 128.63, 127.2, 127.0,
126.3, 125.5, 116.5, 112.2, 40.7, 38.5; HRMS (APCI, positive) calcd
for C17H19BrN ([M + H]+) 316.0701, found 316.0704.
ASSOCIATED CONTENT
■
S
* Supporting Information
Copies of NMR spectra of the products. This material is
available free of charge via the Internet at http://pubs.acs.org.
(E)-4-(1,3-Diphenylallyl)-N,N-dimethylaniline, 4ca. Following
the general procedure, 4ca was obtained as a white solid: mp 79.5−
82.5 °C; 1H NMR (400 MHz, CDCl3) δ 2.91 (s, 6 H), 4.81 (d, J = 7.5
Hz, 1 H), 6.33 (d, J = 15.9 Hz, 1H), 6.65 (dd, J = 15.9, 7.5 Hz, 1 H),
6.70 (d, J = 8.6 Hz, 2 H), 7.10 (d, J = 8.6 Hz, 2 H), 7.17−7.32 (m,
8 H), 7.36 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 40.8,
53.4, 112.8, 126.3, 126.4, 127.2, 128.47, 128.56, 128.72, 129.4, 130.9,
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: qujp@dlut.edu.cn.
Notes
The authors declare no competing financial interest.
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dx.doi.org/10.1021/jo2024812 | J. Org. Chem. 2012, 77, 2942−2946

The Journal of Organic Chemistry
Note
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Nos. 20806012 and 20972022) and the
“111” project of Ministry of Education of China.
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