Pincer-Nickel-Catalyzed Allyl-Aryl Coupling between Allyl Methyl Ethers and Arylzinc Chlorides

Article abstract of DOI:10.1021/acs.joc.5b02151

The P,N,N-pincer nickel complex [Ni(Cl){N(2-Ph₂PC₆H₄)(2′-Me₂NC₆H₄)}]-catalyzed allyl-aryl coupling was studied. The reaction of allyl methyl ethers, including (1-methoxyallyl)arenes and (3-methoxyprop-1-en-1-yl)arenes, with arylzinc chlorides afforded linear (E)-alkenes in high yields, whereas the reaction of (E)-1-methoxytridec-2-ene with p-Me₂NC₆H₄ZnCl generated a mixture of linear and branched alkenes.

Full text of DOI:10.1021/acs.joc.5b02151

Note
pubs.acs.org/joc
Pincer-Nickel-Catalyzed Allyl-Aryl Coupling between Allyl Methyl
Ethers and Arylzinc Chlorides
Jian-Long Tao,† Bo Yang,† and Zhong-Xia Wang*,†,‡
†CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China,
Hefei, Anhui 230026, People’s Republic of China
‡Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, People’s Republic of China
S
* Supporting Information
ABSTRACT: The P,N,N-pincer nickel complex [Ni(Cl){N-
(2-Ph2PC6H4)(2′-Me2NC6H4)}]-catalyzed allyl-aryl coupling
was studied. The reaction of allyl methyl ethers, including (1-
methoxyallyl)arenes and (3-methoxyprop-1-en-1-yl)arenes,
with arylzinc chlorides afforded linear (E)-alkenes in high
yields, whereas the reaction of (E)-1-methoxytridec-2-ene with
p-Me2NC6H4ZnCl generated a mixture of linear and branched
alkenes.
he 1,3-diarylpropenes are useful intermediates in the
Tsynthesis of natural products and biologically active
molecules.1 A powerful synthetic method for 1,3-diarylpropenes
is transition metal-catalyzed allyl-aryl coupling. Allylic halides
and allylic phosphates are often used as electrophilic
The reaction of cinnamyl methyl ether with 4-
substrates.2,3 Recently, allylic alcohol, allylic esters, and allylic
(dimethylamino)phenylzinc chloride was employed to screen
ethers have received considerable attention in these trans-
catalysts and optimize reaction conditions, and the results are
formations. However, reactions of allylic alcohol and allylic
listed in Table S1 in the Supporting Information. The catalytic
esters mainly center on their cross-coupling with organoboron
properties of complexes Ia−Ic were evaluated using similar
reagents.4 A few other coupling reactions of allylic esters, with
reaction conditions to those of the Ia-catalyzed reaction of
organosilicon reagents and copper(I) enolates as well as
aryltrimethylammonium triflates with arylzinc chlorides, which
we reported earlier.10d Thus, the reaction was run in a 2:1
reductive coupling with organic halides, have also been
performed.5 The reported reactions of allylic ethers include
mixture of THF and NMP at 65 °C for 24 h using 0.1 mol % of
catalyst loadings. Each of the complexes was demonstrated to
be catalytically active. Complex Ia resulted in the cross-coupling
product in 82% yield, and Ib and Ic led to 77 and 75% yields,
respectively (entries 1−3, Table S1). Examination of the
reaction temperature showed that the Ia-catalyzed reaction
Suzuki-type coupling,6 Kumada-type coupling,7 and couplings
with organolithium reagents8 or through sp2 C−H bond
activation.9 For example, the reaction of allyl phenyl ethers with
arylboronic acids in water under the catalysis of
PdCl2(DPEphos) affords 3-arylprop-1-enes.6a Allyl methyl
ethers were demonstrated to react with Grignard reagents
under the catalysis of CoCl2/phosphine.7a Despite the excellent
results achieved, investigations on transition metal-catalyzed
allylic arylation of allylic partners is still limited. It is necessary
to further explore the reactivity of allylic alcohol derivatives and
develop a methodology to construct allyl-aryl systems.
In the past several years, we have focused on developing
highly active catalyst systems for transition metal-catalyzed C−
C cross-coupling reactions.10 Recently, we demonstrated that
P,N,N-pincer nickel complexes Ia−Ic can catalyze cross-
couplings of arylzinc reagents with aryl chlorides or
aryltrimethylammonium triflates, and complex Ia exhibited
high catalytic activity.10c,d On the basis of these findings, we
intended to study the reaction of arylzinc reagents with allylic
ethers to synthesize 1,3-diarylpropenes using the pincer nickels
as catalyst.
could not give the desired product at room temperature and
generated a corresponding product in 55% yield at 45 °C and
87% yield at 80 °C, respectively (entries 4−6, Table S1). A
reaction temperature higher than 80 °C cannot further increase
the product yield. Then, we examined the solvent effect using
Ia as the catalyst at 80 °C. A series of solvents, including THF,
THF/toluene (2:1), THF/dioxane (2:1), and THF/DMA
(2:1) were tested (entries 6−10, Table S1). The results showed
that a 2:1 mixture of THF and DMA was the best solvent. 99%
GC yield and 91% isolated yield could be achieved (entry 10,
Table 1). A higher isolated yield (97%) of the cross-coupling
product was achieved when 2.0 equiv of 4-(dimethylamino)-
phenylzinc chloride was used (entry 11, Table S1). In these
Received: September 13, 2015
© XXXX American Chemical Society
A
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Note
were necessary (entries 3−6, Table 1). Several fused arylzinc
reagents, including naphthalen-2-ylzinc chloride, 6-methoxy-
naphthalen-2-ylzinc chloride, and phenanthren-9-ylzinc chlor-
ide, were also tested (entries 7−9, Table 1). They exhibited
good reactivity in the reaction with cinnamyl methyl ether
under the optimized conditions. Each reaction proceeded
smoothly and gave an excellent product yield. The electron-
poor arylzinc reagent 4-(trifluoromethyl)phenylzinc chloride,
heteroarylzinc reagents 2-furylzinc chloride and 2-thienylzinc
chloride, and alkylzinc reagent 3-phenylpropylzinc chloride
were also tested for catalyzed cross-coupling with cinnamyl
methyl ether. However, none of them gave the desired cross-
coupling product, and the ether was not consumed in these
reactions. 4-(Trifluoromethyl)phenylzinc chloride has lower
nucleophility compared with those of the substituted phenyl-
zinc reagents mentioned above. The weak nucleophility may
lead to failure of the transmetalation reaction in the catalytic
cycle (see below). Both 2-furylzinc chloride and 2-thienylzinc
chloride are electron-rich nucleophilic reagents. However, the
Lewis acids in the system, such as LiCl, MgCl2, and ZnCl2 may
combine with the 2-furyl and 2-thienyl groups through
coordination. The combination results in a decrease of their
nucleophility. In the case of 3-phenylpropylzinc chloride, we
guess that the unsuccessful reaction may be due to a difficult
reductive elimination in the catalytic process.
Table 1. Ia-Catalyzed Cross-Coupling of (E)-(3-
Methoxyprop-1-en-1-yl)benzene with Arylzinc Chlorides
a
Furthermore, we examined the reactivity of various branched
ethers using 4-(dimethylamino)-phenylzinc chloride as the
nucleophilic reagent. When 3-aryl-3-methoxy-prop-1-enes were
used as the electrophiles to react with 4-(dimethylamino)-
phenylzinc chloride under the optimized conditions, (E)-N,N-
dimethyl-4-(3-arylallyl)aniline (1 and 10−17) rather than N,N-
dimethyl-4-(1-arylallyl) aniline were formed (Scheme 1). That
is to say, allylic rearrangements occurred in the reaction process
to selectively provide linear rather than branched coupling
products. In addition, among these substrates, both 1-methoxy-
2-(1-methoxyallyl)benzene and 2-(1-methoxyallyl)thiophene
exhibited relatively low reactivity. The former gave lower
product yield (77%) compared with other substrates under the
same conditions, and the latter required higher catalyst loading
(1 mol % of Ia) to drive the reaction to completion. This may
be due to steric hindrance of the substrate for the former and
catalyst poisoning by the thienyl group for the latter. The
reaction tolerated functional groups, such as C(O)OEt,
C(O)NEt2, and F groups. However, the reaction of 1-chloro-
4-(1-methoxyallyl)benzene with 4-(dimethylamino)phenylzinc
chloride gave a mixture of (E)-4-(3-(4-chlorophenyl)allyl)-N,N-
dimethylaniline (18) and (E)-4′-(3-(4-(dimethylamino)-
phenyl)prop-1-enyl)-N,N-dimethylbiphenyl-4-amine (19) in
58 and 11% isolated yield, respectively (Scheme 2). From the
product distribution, it seems that the allyl C−O bond is more
reactive than the aryl C−Cl bond.
Reactivity of several 1-aryl-3-alkyl-3-methoxypropenes was
also examined, and the results are presented in Scheme 3. The
reaction of 1-phenyl-3-alkyl-3-methoxypropenes with 4-
(dimethylamino)phenylzinc chloride proceeded smoothly
under the optimized conditions, and no allylic rearrangements
were observed whether the alkyl group is Me, Et, nBu, or iPr.
However, bulkier alkyl groups in the electrophilic substrates
result in lower product yields. For example, the reaction of the
3-position methyl derivative with 4-(dimethylamino)phenylzinc
chloride gave 91% yield of cross-coupling product 20, but the
reaction of the 3-position isopropyl derivative gave 80%
product yield. Heteroarylallyl methyl ether (E)-2-(3-methox-
a
The reactions were carried out using 0.5 mmol cinnamyl methyl ether
and 1.0 mmol arylzinc chloride according to the conditions indicated
by the above equation; the zinc reagents were prepared from
corresponding Grignard reagents and ZnCl2 in the presence of 2
b
c
equiv of LiCl. Isolated yield. Catalyst loading of 0.01 mol %.
reactions, a homocoupling product of the zinc reagent was also
observed. In the absence of a nickel catalyst, the reaction
cannot give any desired product (entry 12, Table S1). In
addition, a test of the salt effect showed that the zinc reagent, 4-
(dimethylamino)phenylzinc chloride, prepared from the
corresponding Grignard reagent and ZnCl2 in the presence of
2 equiv of LiCl, gave a better reaction result than those
prepared from p-Me2NC6H4Li and ZnCl2, p-Me2NC6H4MgBr
and ZnCl2, or p-Me2NC6H4Li and ZnCl2 in the presence of 1
equiv of MgBr2 (entries 13−15, Table S1). This implies that
both lithium and magnesium ions play important roles in the
reaction. This may be due to the presence of a multimetallic
synergistic effect in the reaction process.11 The role of LiCl
additive may also involve breaking the aggregation of ArZnCl
with the coproduct MgCl2 through forming a trimetallic adduct
and enhancing the reactivity of the zinc reagents by forming
more nucleophilic zincates.11,12
Next, we examined cross-coupling of cinnamyl methyl ether
with different arylzinc reagents under the optimized reaction
conditions. 4-Methoxyphenylzinc chloride exhibited similar
reactivity to 4-(dimethylamino)phenylzinc chloride. As elec-
tron-rich nucleophiles, both 4-(dimethylamino)phenylzinc
chloride and 4-methoxyphenylzinc chloride can react smoothly
with cinnamyl methyl ether in the presence of 0.01 mol % of Ia,
giving corresponding products 1 and 2 in excellent yields
(entries 1 and 2, Table 1). Similar reactions using benzo[1,3]-
dioxol-5-ylzinc chloride, p-tolylzinc chloride, phenylzinc
chloride, and (1,1′-biphenyl)-4-ylzinc chloride as nucleophiles
also led to high product yields, but 0.1 mol % catalyst loadings
B
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Scheme 1. Ia-Catalyzed Cross-Coupling of 3-Aryl-3-
methoxy-prop-1-enes with p-Me2NC6H4ZnCl
Scheme 3. Ia-Catalyzed Cross-Coupling of 1-Aryl-3-alkyl-3-
methoxypropenes with p-Me2NC6H4ZnCl
a
a
a
The reactions were carried out on a 0.5 mmol scale, and 2.0 equiv of
zinc reagent was employed. The zinc reagents were prepared from
corresponding Grignard reagents and ZnCl2 in the presence of 2 equiv
of LiCl. Isolated product yields are reported.
Scheme 4. Sequential Cross-Coupling of 1-Fluoro-4-(1-
methoxyallyl)benzene
a
The reactions were carried out on a 0.5 mmol scale, and 2.0 equiv of
zinc reagent was employed. The zinc reagents were prepared from
corresponding Grignard reagents and ZnCl2 in the presence of 2 equiv
b
of LiCl. Isolated product yields are reported. Ia was employed at 1
mol %.
Scheme 2. Ia-Catalyzed Reaction of 1-Chloro-4-(1-
methoxyallyl)benzene with p-Me2NC6H4ZnCl
of the cross-coupling product. This ruled out the possibility of a
free radical mechanism. No reaction occurred between
cinnamyl methyl ether and an equiv of Ia in THF at 80 °C
(bath temperature). However, a reaction between cinnamyl
methyl ether and an equiv of Ni(0) species prepared in situ
from Ni(COD)2 and lithiated (2-Ph2PC6H4)NH(2′-
Me2 NC6 H4 ), supposing [Li{N(2-Ph2 PC6 H4 )(2′-
Me2NC6H4)}] (II) did occur in THF at 80 °C, and cinnamyl
methyl ether was completely consumed in 24 h. Attempts to
isolate the formed nickel complexes were unsuccessful. The
combination of Ni(COD)2 and II effectively catalyzed the
cross-coupling of cinnamyl methyl ether with p-
Me2NC6H4ZnCl in THF/DMA (2:1) at 80 °C and 0.1 mol
% Ni(COD)2/II, leading to the desired product in 95% yield.
These experimental facts showed that the catalytically active
species may be a Ni(0) complex. The allylic rearrangements
shown in Scheme 1 support a π-allylnickel intermediate formed
in the catalytic process. A proposed catalytic cycle is outlined in
Scheme 5. In the catalytic cycle, the tridentate ligand may be
hemilabile. In intermediates B and C, the ligand is expected to
adopt a didentate coordination mode, which keeps an 18e
configuration of the central metals in the intermediates.
ybut-1-en-1-yl)furan was also demonstrated to be a good
electrophile in the cross-coupling. Its reaction with 4-
(dimethylamino)phenylzinc chloride afforded (E)-4-(4-(furan-
2-yl)but-3-en-2-yl)-N,N-dimethylaniline 24 in 86% yield.
As shown in Scheme 1, the catalytic reaction can tolerate the
CAr−F bond in the arylallyl ether. Our previous work showed
that the CAr−F bond can be catalytically cleaved and coupled to
a zinc reagent using Ni(PCy3)2Cl2 as catalyst.10 Hence, we tried
to install two different aryl groups into the fluorated arylallyl
ether in a one-pot reaction. The results demonstrated that the
reaction could be performed well and gave 74% overall yield
(Scheme 4). The nickel complex Ia used in the first step did
not affect the following reaction. The excess zinc reagent in the
first step was consumed due to its homocoupling.
The regioselectivity of the reactions is probably the result of
both maximizing conjugation and minimizing steric hindrance
in the coupling of the zinc reagent with the putative π-
allylnickel intermediate, and the conjugation seems to act
predominantly. This conjecture is supported by the reactions
shown in Schemes 3 and 6. In the reaction shown in Scheme 6,
the aliphatic group substituted allyl methyl ether (E)-1-
The Ia-catalyzed reaction of cinnamyl methyl ether with p-
Me2NC6H4ZnCl was not affected by the 1,1-diphenylethene
additive. The reaction run under the optimized conditions in
the presence of 1,1-diphenylethene (1.0 equiv) gave 95% yield
C
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THF, 9.0 mmol) was added dropwise to a stirred solution of
benzaldehyde (0.61 mL, 6.00 mmol) in THF (15 mL) at −78 °C. The
resulting solution was warmed to room temperature and stirred for 4
h. Ice water (20 mL) was added slowly to the mixture after which ethyl
acetate (20 mL) was added. The organic layer was separated, and the
aqueous phase was extracted with ethyl acetate (2 × 20 mL). The
combined organic phase was washed with brine (20 mL), dried over
MgSO4, and evaporated to dryness by rotary evaporation to give 1-
phenylprop-2-en-1-ol with a yield of 0.44 g (55%). This product was
used in the next step without further purification.
Scheme 5. A Proposed Catalytic Cycle
1-Phenylprop-2-en-1-ol (0.44 g, 3.28 mmol) was dissolved in THF
(10 mL) and added dropwise to a stirred suspension of NaH (0.27 g,
60% dispersion in mineral oil, 6.75 mmol) in THF (15 mL) at 0 °C.
The mixture was warmed to room temperature and stirred for 1 h.
Then, MeI (0.62 mL, 9.96 mmol) was added dropwise to the stirred
mixture. The resulting mixture was stirred overnight at room
temperature. Ice water (20 mL) was added slowly to the mixture
after which ethyl acetate (20 mL) was added. The organic layer was
separated, and the aqueous phase was extracted with ethyl acetate (2 ×
20 mL). The combined organic phase was then washed with brine (20
mL), dried over MgSO4, and evaporated to dryness by rotary
evaporation. The residue was purified by column chromatography
(eluted with petroleum ether/EtOAc (100:1 v/v)) to yield (1-
methoxyallyl)benzene as a clear oil with a yield of 0.46 g (52% overall
yield). 1H NMR (400 MHz, CDCl3): δ 3.33 (d, J = 1.1 Hz, 3H), 4.62
(d, J = 6.7 Hz, 1H), 5.19−5.30 (m, 2H), 5.89−5.98 (m, 1H), 7.26−
7.38 (m, 5H). 13C NMR (101 MHz, CDCl3): δ 56.4, 84.7, 116.3,
126.8, 127.7, 128.4, 138.8, 140.9.
Scheme 6. Ia-Catalyzed Reaction of (E)-1-Methoxytridec-2-
ene with p-Me2NC6H4ZnCl
methoxytridec-2-ene with p-Me2NC6H4ZnCl resulted in a
The same procedure as for (1-methoxyallyl)benzene was used to
prepare the other 3-aryl-3-methoxyprop-1-enes.
mixture of linear and branched regioisomers in a ratio of
1
69:31 (based on H NMR integration), whereas the reactions
1-Methoxy-3-(1-methoxyallyl)benzene. Eluent: petroleum ether/
of the aryl group substituted allyl methyl ether with p-
Me2NC6H4ZnCl gave only linear isomers.
1
EtOAc (60:1 v/v). Colorless oil, yield 0.74 g (69%). H NMR (400
MHz, CDCl3): δ 3.33 (s, 3H), 3.81 (s, 3H), 4.59 (d, J = 6.7 Hz, 1H),
5.19−5.22 (m, 1H), 5.28 (dt, J = 16.8, 1.2 Hz, 1H), 5.88−5.96 (m,
1H), 6.81−6.84 (m, 1H), 6.88−6.92 (m, 2H), 7.26 (t, J = 7.9 Hz, 1H).
13C NMR (101 MHz, CDCl3): δ 55.2, 56.4, 84.6, 112.1, 113.3, 116.3,
119.2, 129.4, 138.6, 142.5, 159.8. HR-MS: m/z 179.10701 [M + H]+;
calcd for C11H15O2, 179.10666.
In summary, we have demonstrated a pincer-nickel complex
[Ni(Cl){N(2-Ph2PC6H4)(2′-Me2NC6H4)}] (Ia) that can
effectively catalyze cross-coupling of allyl methyl ethers with
arylzinc reagents under mild conditions with low catalyst
loadings. The reaction shows high regioselectivity when (1-
methoxyallyl)arenes or (3-methoxyprop-1-en-1-yl)arenes were
employed as the electrophilic substrates, giving linear (E)-
alkenes in high yields. Aliphatic group substituted allyl methyl
ether (E)-1-methoxytridec-2-ene also exhibited good reactivity
with p-Me2NC6H4ZnCl under the same conditions but formed
a mixture of linear and branched regioisomers. The reaction
may proceed through a Ni(0)/Ni(II) process with π-allylnickel
intermediates, but the exact mechanism is not presently clear.
4-(1-Methoxyallyl)-N,N-dimethylaniline. Eluent: petroleum ether/
1
EtOAc (60:1 v/v). Colorless oil, yield 0.49 g (42%). H NMR (400
MHz, CDCl3): δ 2.94 (s, 6H), 3.29 (s, 3H), 4.54 (d, J = 6.5 Hz, 1H),
5.16 (dt, J = 10.4, 1.2 Hz, 1H), 5.24 (dt, J = 17.2, 1.4 Hz, 1H), 5.91−
6.00 (m, 1H), 6.72 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.8 Hz, 2H). 13C
NMR (101 MHz, CDCl3): δ 40.6, 56.0, 84.4, 112.5, 115.4, 127.9,
128.5, 139.2, 150.3. HR-MS: m/z 192.13924 [M + H]+; calcd for
C12H18NO, 192.13829.
1-Methoxy-2-(1-methoxyallyl)benzene. Eluent: petroleum ether/
1
EtOAc (60:1 v/v). Colorless oil, yield 0.38 g (36%). H NMR (400
EXPERIMENTAL SECTION
MHz, CDCl3): δ 3.33 (s, 3H), 3.83 (s, 3H), 5.10 (d, J = 6.3 Hz, 1H),
5.12−5.15 (m, 1H), 5.24−5.29 (m, 1H), 5.89−5.98 (m, 1H), 6.88 (dd,
J = 8.3, 0.9 Hz, 1H), 6.98 (dt, J = 7.6, 1.1 Hz, 1H), 7.23−7.27 (m, 1H),
7.37 (dd, J = 7.6, 1.8 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 55.4,
56.5, 77.9, 110.6, 115.3, 120.8, 127.0, 128.5, 129.2, 138.1, 156.8. HR-
MS: m/z 179.10614 [M + H]+; calcd for C11H15O2, 179.10666.
1-(1-Methoxyallyl)naphthalene.18 Eluent: petroleum ether/EtOAc
■
General Information. All air- or moisture-sensitive manipulations
were performed under nitrogen using standard Schlenk techniques.
Toluene and dioxane were distilled under nitrogen over sodium; THF
was distilled under nitrogen over sodium/benzophenone; NMP and
DMA were dried over 4 Å molecular sieves, fractionally distilled under
reduced pressure, and stored under a nitrogen atmosphere. N,N-
Diethyl-4-formylbenzamide,13 ethyl 4-(1-hydroxyallyl)benzoate,14 (E)-
(3-methoxyprop-1-en-1-yl)benzene,9b 1-fluoro-4-(1-methoxyallyl)-
benzene,15 and 1-chloro-4-(1-methoxyallyl)benzene15 were prepared
according to literature procedures. Grignard reagents were prepared
according to reported methods.16 Arylzinc chlorides were prepared
from ZnCl2 and an equiv of ArMgBr in the presence of 2 equiv of LiCl.
All other chemicals and solvents were obtained from commercial
vendors and used as received. NMR spectra were recorded on a 400
MHz NMR spectrometer at ambient temperature. The chemical shifts
1
(100:1 v/v). Colorless oil, yield 0.97 g (82%). H NMR (400 MHz,
CDCl3): δ 3.39 (s, 3H), 5.21−5.26 (m, 1H), 5.29−5.36 (m, 2H),
6.10−6.19 (m, 1H), 7.45−7.52 (m, 3H), 7.56 (d, J = 7.1 Hz, 1H), 7.80
(d, J = 8.1 Hz, 1H), 7.84−7.88 (m, 1H), 8.16−8.21 (m, 1H). 13C
NMR (101 MHz, CDCl3): δ 56.6, 82.7, 116.7, 124.0, 124.9, 125.4,
125.5, 125.9, 128.4, 128.8, 131.0, 134.0, 136.2, 138.1.
2-(1-Methoxyallyl)thiophene. Eluent: petroleum ether/EtOAc
(100:1 v/v). Yellow oil, 0.36 g (39%). 1H NMR (400 MHz,
CDCl3): δ 3.36 (s, 3H), 4.87 (d, J = 6.8 Hz, 1H), 5.28 (dt, J =
10.0, 1.2 Hz, 1H), 5.35 (dt, J = 17.2, 1.3 Hz, 1H), 5.94−6.03 (m, 1H),
6.96−6.98 (m, 2H), 7.26−7.29 (m, 1H). 13C NMR (101 MHz,
CDCl3): δ 56.3, 80.2, 117.2, 124.9, 125.3, 126.5, 137.8, 144.5. HR-MS:
m/z 123.02583 [M-MeO]+; calcd for C7H7S, 123.02630.
1
of H NMR spectra were referenced to TMS, and the chemical shifts
of 13C NMR spectra were referenced to internal solvent resonances
(δCDCl3 = 77.0 ppm). High-resolution mass spectra (HR-MS) were
acquired in ESI mode using an Orbitrap mass analyzer.
Synthesis of (E)-(3-Methoxybut-1-en-1-yl)benzene.19 MeLi (6.3
mL, 1.3 M solution in Et2O, 8.19 mmol) was added dropwise to a
Synthesis of Allyl Methyl Ethers. Synthesis of (1-Methoxyallyl)-
benzene.17 Vinylmagnesium bromide (9.0 mL, 1.0 M solution in
D
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solution of cinnamaldehyde (0.95 mL, 7.54 mmol) in Et2O (15 mL) at
−78 °C with stirring. The resulting mixture was warmed to room
temperature and stirred for 4 h. Ice water (20 mL) was added slowly to
the mixture. The organic layer was separated, and the aqueous phase
was extracted with ethyl acetate (3 × 15 mL). The combined organic
phase was washed with brine (20 mL), dried over MgSO4, and
evaporated to dryness by rotary evaporation to give (E)-4-phenylbut-
3-en-2-ol with a yield of 0.943 g (85%). This product was used in the
next step without further purification.
A solution of (E)-4-phenylbut-3-en-2-ol (0.943 g, 6.36 mmol) in
THF (10 mL) was added dropwise to a stirred suspension of NaH
(0.51 g, 60% dispersion in mineral oil, 12.75 mmol) in THF (15 mL)
at 0 °C. The mixture was warmed to room temperature and stirred for
1 h. Then, MeI (1.2 mL, 19.27 mmol) was added dropwise to the
mixture. The resulting mixture was stirred overnight at room
temperature. Ice water (20 mL) was added slowly to the mixture
after which ethyl acetate (20 mL) was added. The organic layer was
separated, and the aqueous phase was extracted with ethyl acetate (2 ×
20 mL). The combined organic phase was washed with brine (20 mL),
dried over MgSO4, and evaporated to dryness by rotary evaporation.
The residue was purified by column chromatography (eluted with
petroleum ether/EtOAc (100:1 v/v)) to yield (E)-(3-methoxybut-1-
en-1-yl)benzene as a clear oil with a yield of 0.93 g (76% overall yield).
1H NMR (400 MHz, CDCl3): δ 1.33 (d, J = 6.3 Hz, 3H), 3.32 (s, 3H),
3.86−3.93 (m, 1H), 6.09 (dd, J = 16.0, 7.7 Hz, 1H), 6.53 (d, J = 16.0
Hz, 1H), 7.21−7.27 (m, 1H), 7.32 (t, J = 7.5 Hz, 2H), 7.38−7.41 (m,
2H). 13C NMR (101 MHz, CDCl3): δ 21.5, 56.0, 78.1, 126.4, 127.6,
128.6, 131.3, 131.4, 136.6.
h. Ice water (15 mL) was added slowly to the mixture after which ethyl
acetate (15 mL) was added. The organic layer was separated, and the
aqueous phase was extracted with ethyl acetate (2 × 15 mL). The
combined organic phase was washed with brine (15 mL), dried over
MgSO4, and evaporated to dryness by rotary evaporation to give N,N-
diethyl-4-(1-hydroxyallyl)benzamide with a yield of 0.49 g (53%). This
product was used in the next step without further purification.
N,N-Diethyl-4-(1-hydroxyallyl)benzamide (0.49 g, 2.1 mmol) was
dissolved in THF (4 mL) and added dropwise to a stirred suspension
of NaH (0.13 g, 60% dispersion in mineral oil, 3.15 mmol) in THF (5
mL) at 0 °C. The mixture was warmed to room temperature and
stirred for 1 h. MeI (0.4 mL, 6.3 mmol) was added dropwise to the
stirred mixture. The resulting mixture was stirred overnight at room
temperature. Ice water (10 mL) was added slowly to the mixture after
which ethyl acetate (10 mL) was added. The organic layer was
separated, and the aqueous phase was extracted with ethyl acetate (2 ×
10 mL). The combined organic phase was then washed with brine (10
mL), dried over MgSO4, and evaporated to dryness by rotary
evaporation. The residue was purified by column chromatography
(eluted with petroleum ether/EtOAc (4:1 v/v)) to give N,N-diethyl-4-
(1-methoxyallyl)benzamide as a clear oil with a yield of 0.44 g (85%).
1H NMR (400 MHz, CDCl3): δ 1.11 (b, 3H), 1.25 (b, 3H), 3.26 (b,
2H), 3.35 (s, 3H), 3.54 (b, 2H), 4.64 (d, J = 6.9 Hz, 1H), 5.24 (d, J =
10.3 Hz, 1H), 5.30 (d, J = 17.2 Hz, 1H), 5.85−5.94 (m, 1H), 7.36 (s,
4H). 13C NMR (101 MHz, CDCl3): δ 12.9, 14.2, 39.2, 43.3, 56.4, 84.3,
116.8, 126.5, 126.8, 136.5, 138.3, 141.9, 171.1. HR-MS: m/z
248.16476 [M + H]+; calcd for C15H22O2N, 248.16451.
Synthesis of Ethyl 4-(1-Methoxyallyl)benzoate. NaH (0.12 g, 60%
dispersion in mineral oil, 3.0 mmol) was added to a stirred solution of
ethyl 4-(1-hydroxyallyl)benzoate (0.41 g, 2.0 mmol) and MeI (0.50
mL, 8.0 mmol) in THF (6 mL) at 0 °C in one portion. The resulting
mixture was stirred at 0 °C for 30 min and then stirred overnight at
room temperature. Ice water (10 mL) was added slowly to the mixture
after which ethyl acetate (10 mL) was added. The organic layer was
separated, and the aqueous phase was extracted with ethyl acetate (2 ×
10 mL). The combined organic phase was washed with brine (10 mL),
dried over MgSO4, and evaporated to dryness by rotary evaporation.
The residue was purified by column chromatography (eluted with
petroleum ether/EtOAc (60:1 v/v)) to afford ethyl 4-(1-
methoxyallyl)benzoate as a clear oil with a yield of 0.24 g (54%).
1H NMR (400 MHz, CDCl3): δ 1.39 (t, J = 7.2 Hz, 3H), 3.34 (s, 3H),
The same procedure as for (E)-(3-methoxybut-1-en-1-yl)benzene
was used to prepare the other (3-alkyl-3-methoxyprop-1-en-1-
yl)benzenes and 2-(3-methoxybut-1-en-1-yl)furan.
(E)-(3-Methoxypent-1-en-1-yl)benzene.20 Eluent: petroleum
ether/EtOAc (100:1 v/v). Colorless oil, yield 0.95g (72%). 1H
NMR (400 MHz, CDCl3): δ 0.93 (t, J = 7.5 Hz, 3H), 1.53−1.65 (m,
1H), 1.66−1.78 (m, 1H), 3.32 (s, 3H), 3.62 (q, J = 7.2 Hz, 1H), 6.04
(dd, J = 16.0, 8.0 Hz, 1H), 6.53 (d, J = 16.0 Hz, 1H), 7.22−7.27 (m,
1H), 7.33 (t, J = 7.5 Hz, 2H), 7.40 (d, J = 7.1 Hz, 2H). 13C NMR (101
MHz, CDCl3): δ 9.8, 28.5, 56.3, 84.0, 126.4, 127.6, 128.6, 130.3, 132.4,
136.7. HR-MS: m/z 177.12757 [M + H]+; calcd for C12H17O,
177.12739.
(E)-(3-Methoxyhept-1-en-1-yl)benzene. Eluent: petroleum ether/
1
EtOAc (100:1 v/v). Colorless oil, yield 1.19 g (78%). H NMR (400
4.37 (q, J = 7.2 Hz, 2H), 4.67 (d, J = 6.8 Hz, 1H), 5.24 (dt, J = 1.2,
10.4 Hz, 1H), 5.30 (dt, J = 1.4, 17.2 Hz, 1H), 5.84−5.92 (m, 1H), 7.40
(d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.4 Hz, 2H). 13C NMR (101 MHz,
CDCl3): δ 14.3, 56.5, 60.9, 84.3, 117.2, 126.6, 129.7, 129.8, 138.1,
145.9, 166.4. HR-MS: m/z 221.11687 [M + H]+; calcd for C13H17O3,
221.11722.
Synthesis of (E)-1-Methoxytridec-2-ene. (E)-1-Methoxytridec-2-
ene was prepared on a 6 mmol scale according to the second step of
the procedure for (E)-(3-methoxybut-1-en-1-yl)-benzene. (E)-1-
Methoxytridec-2-ene was purified by column chromotography (eluted
with petroleum ether/EtOAc (100:1 v/v)) to give a pale yellow oil
with a yield of 1.03 g (81%). 1H NMR (400 MHz, CDCl3): δ 0.88 (t, J
= 6.8 Hz, 3H), 1.20−1.43 (m, 16H), 2.04 (q, J = 7.0 Hz, 2H), 3.32 (s,
3H), 3.86 (d, J = 6.3 Hz, 2H), 5.50−5.59 (m, 1H), 5.66−5.75 (m,
1H). 13C NMR (101 MHz, CDCl3): δ 14.1, 22.7, 29.1, 29.2, 29.3, 29.5,
29.59, 29.61, 31.9, 32.3, 57.6, 73.3, 126.0, 135.1. HR-MS: m/z
213.22104 [M + H]+; calcd for C14H29O, 213.22129.
General Procedure for the Cross-Coupling of Allyl Methyl
Ethers with Arylzinc Chlorides. A Schlenk tube was charged with
allyl methyl ether (0.5 mmol), DMA (1.05 mL), and a solution of
complex Ia (0.1 mL, 0.005 M solution in THF, 0.0005 mmol). To the
stirred mixture was added ArZnCl solution (2 mL, 0.5 M solution in
THF, 1.0 mmol) by syringe. The reaction mixture was stirred at 80 °C
for 24 h. Water (10 mL) and several drops of glacial acetic acid were
added successively. The mixture was extracted with ethyl acetate (3 ×
10 mL). The combined organic phases were dried over anhydrous
Na2SO4, concentrated by rotary evaporation, and purified by column
chromatography (silica gel).
MHz, CDCl3): δ 0.90 (t, J = 7.0 Hz, 3H), 1.27−1.42 (m, 4H), 1.50−
1.62 (m, 1H), 1.63−1.76 (m, 1H), 3.31 (s, 3H), 3.68 (q, J = 7.2 Hz,
1H), 6.05 (dd, J = 15.9, 8.0 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H), 7.22−
7.26 (m, 1H), 7.33 (t, J = 7.5 Hz, 2H), 7.40 (d, J = 7.0 Hz, 2H). 13C
NMR (101 MHz, CDCl3): δ 14.0, 22.7, 27.6, 35.4, 56.2, 82.7, 126.4,
127.6, 128.6, 130.6, 132.2, 136.7. HR-MS: m/z 205.15914 [M + H]+;
calcd for C14H21O, 205.15869.
(E)-(3-Methoxy-4-methylpent-1-en-1-yl)benzene. Eluent: petrole-
1
um ether/EtOAc (100:1 v/v). Colorless oil, yield 0.88 g (62%). H
NMR (400 MHz, CDCl3): δ 0.91 (d, J = 6.8 Hz, 3H), 0.97 (d, J = 6.7
Hz, 3H), 1.81−1.89 (m, 1H), 3.31 (s, 3H), 3.39 (dd, J = 7.8, 6.6 Hz,
1H), 6.06 (dd, J = 16.0, 8.2 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 7.22−
7.27 (m, 1H), 7.33 (t, J = 7.5 Hz, 2H), 7.41 (d, J = 7.4 Hz, 2H). 13C
NMR (101 MHz, CDCl3): δ 18.3, 18.7, 33.0, 56.6, 88.1, 126.4, 127.6,
128.6, 128.8, 133.1, 136.8. HR-MS: m/z 191.14351 [M + H]+; calcd
for C13H19O, 191.14304.
(E)-2-(3-Methoxybut-1-en-1-yl)furan. Eluent: petroleum ether/
1
EtOAc (100:1 v/v). Yellow oil, yield 0.77 g (67%). H NMR (400
MHz, CDCl3): δ 1.31 (d, J = 6.4 Hz, 3H), 3.31 (s, 3H), 3.81−3.89 (m,
1H), 6.04 (dd, J = 15.9, 7.5 Hz, 1H), 6.24 (d, J = 3.3 Hz, 1H), 6.34−
6.38 (m, 2H), 7.35 (d, J = 1.7 Hz, 1H). 13C NMR (101 MHz, CDCl3):
δ 21.4, 56.1, 77.7, 107.8, 111.2, 119.5, 130.2, 141.9, 152.3. HR-MS: m/
z 153.09103 [M + H]+; calcd for C9H13O2, 153.09101.
Synthesis of N,N-diethyl-4-(1-methoxyallyl)benzamide. Vinyl-
magnesium bromide (4.2 mL, 1.0 M solution in THF, 4.2 mmol)
was added dropwise to a stirred solution of N,N-diethyl-4-
formylbenzamide (0.82 g, 4.0 mmol) in THF (8 mL) at 0 °C. The
resulting solution was warmed to room temperature and stirred for 4
E
DOI: 10.1021/acs.joc.5b02151
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
4-Cinnamyl-N,N-dimethylaniline (1).21 Eluent: petroleum ether/
EtOAc (60:1 v/v), yield of 0.115 g (97%). 1H NMR (400 MHz,
CDCl3): δ 2.92 (s, 6H), 3.46 (d, J = 6.4 Hz, 2H), 6.34 (dt, J = 15.6, 6.4
Hz, 1H), 6.43 (d, J = 15.6 Hz, 1H), 6.72 (d, J = 8.7 Hz, 2H), 7.12 (d, J
= 8.4 Hz, 2H), 7.18 (t, J = 7.3 Hz, 1H), 7.28 (t, J = 7.6 Hz, 2H), 7.35
(d, J = 7.1 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 38.4, 40.9, 113.1,
126.1, 126.9, 128.2, 128.4, 129.3, 130.2, 130.3, 137.7, 149.3.
112.7, 113.0, 118.8, 128.1, 129.3, 129.4, 130.2, 130.5, 139.2, 149.3,
159.8. HR-MS: m/z 268.16965 [M + H]+; calcd for C18H22NO,
268.16959.
(E)-4,4′-(Prop-1-ene-1,3-diyl)bis(N,N-dimethylaniline) (11). Elu-
ent: petroleum ether/EtOAc (50:1 v/v). Colorless oil, yield 0.118 g
1
(84%). H NMR (400 MHz, CDCl3): δ 2.91 (s, 6H), 2.93 (s, 6H),
3.42 (d, J = 6.8 Hz, 2H), 6.13 (dt, J = 15.7, 6.9 Hz, 1H), 6.35 (d, J =
15.7 Hz, 1H), 6.66 (d, J = 8.8 Hz, 2H), 6.71 (d, J = 8.6 Hz, 2H), 7.12
(d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.8 Hz, 2H). 13C NMR (101 MHz,
CDCl3): δ 38.4, 40.6, 41.9, 112.6, 113.1, 126.0, 126.5, 126.9, 129.0,
129.2, 130.2, 149.2, 149.7. HR-MS: m/z 281.20126 [M + H]+; calcd
for C19H25N2, 281.20123.
1-Cinnamyl-4-methoxybenzene (2).4d Eluent: petroleum ether/
EtOAc (100:1 v/v), yield 0.108 g (96%). 1H NMR (400 MHz,
CDCl3): δ 3.48 (d, J = 6.5 Hz, 2H), 3.79 (s, 3H), 6.33 (dt, J = 15.6, 6.4
Hz, 1H), 6.43 (d, J = 15.6 Hz, 1H), 6.85 (d, J = 8.7 Hz, 2H), 7.15 (d, J
= 8.8 Hz, 2H), 7.18−7.21 (m, 1H), 7.28 (t, J = 7.6 Hz, 2H), 7.33−7.36
(m, 2H). 13C NMR (101 MHz, CDCl3): δ 38.4, 55.3, 113.9, 126.1,
127.0, 128.5, 129.6, 129.7, 130.7, 132.1, 137.5, 158.0.
(E)-4-(3-(2-Methoxyphenyl)allyl)-N,N-dimethylaniline (12). Elu-
ent: petroleum ether/EtOAc (60:1 v/v). White solid, yield 0.103 g
5-Cinnamylbenzo[d][1,3]dioxole (3).22 Eluent: petroleum ether/
EtOAc (100:1 v/v), yield 0.106 g (89%). 1H NMR (400 MHz,
CDCl3): δ 3.45 (d, J = 6.7 Hz, 2H), 5.91 (s, 2H), 6.30 (dt, J = 15.8, 6.7
Hz, 1H), 6.43 (d, J = 15.8 Hz, 1H), 6.65−6.78 (m, 3H), 7.17−7.22
(m, 1H), 7.28 (t, J = 7.5 Hz, 2H), 7.35 (d, J = 7.3 Hz, 2H). 13C NMR
(101 MHz, CDCl3): δ 39.0, 100.8, 108.2, 109.2, 121.4, 126.1, 127.1,
128.5, 129.3, 131.0, 133.9, 137.4, 145.9, 147.7.
1
(77%); mp 68−70 °C. H NMR (400 MHz, CDCl3): δ 2.91 (s, 6H),
3.48 (d, J = 7.0 Hz, 2H), 3.83 (s, 3H), 6.33 (dt, J = 15.8, 7.1 Hz, 1H),
6.71 (d, J = 8.8 Hz, 2H), 6.79 (d, J = 15.8 Hz, 1H), 6.82−6.91 (m,
2H), 7.12 (d, J = 8.8 Hz, 2H), 7.14−7.20 (m, 1H), 7.41 (dd, J = 7.6,
1.7 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 38.9, 40.9, 55.4, 110.8,
113.1, 120.6, 125.0, 126.6, 126.8, 127.9, 128.6, 129.2, 130.8, 149.3,
156.4. HR-MS: m/z 268.16943 [M + H]+; calcd for C18H22NO,
268.16959.
1-Cinnamyl-4-methylbenzene (4).4d Eluent: petroleum ether, yield
0.095 g (91%). 1H NMR (400 MHz, CDCl3): δ 2.33 (s, 3H), 3.51 (d,
J = 6.5 Hz, 2H), 6.34 (dt, J = 15.7, 6.5 Hz, 1H), 6.44 (d, J = 15.8 Hz,
1H), 7.13 (s, 4H), 7.19 (t, J = 7.2 Hz, 1H), 7.28 (t, J = 7.5 Hz, 2H),
7.35 (d, J = 7.8 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 21.0, 38.9,
126.1, 127.0, 128.5, 128.5, 129.2, 129.5, 130.8, 135.7, 137.1, 137.5.
(E)-Prop-1-ene-1,3-diyldibenzene (5).23 Eluent: petroleum ether,
(E)-4-(3-(4-(Dimethylamino)phenyl)prop-1-enyl)-N,N-diethylben-
zamide (13). Eluent: petroleum ether/EtOAc (4:1 v/v). Colorless oil,
1
yield 0.146 g (87%). H NMR (400 MHz, CDCl3): δ 1.09 (b, 3H),
1.22 (b, 3H), 2.91 (s, 6H), 3.24 (b, 2H), 3.45 (d, J = 5.2 Hz, 2H), 3.52
(b, 2H), 6.34−6.44 (m, 2H), 6.71 (d, J = 8.8 Hz, 2H), 7.10 (d, J = 8.8
Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H). 13C NMR
(101 MHz, CDCl3): δ 12.8, 14.1, 38.3, 39.1, 40.7, 43.2, 112.9, 125.8,
126.5, 127.6, 129.2, 129.4, 131.4, 135.4, 138.4, 149.2, 171.1. HR-MS:
m/z 337.22699 [M + H]+; calcd for C22H29ON2, 337.22744.
1
yield 0.086 g (89%). H NMR (400 MHz, CDCl3): δ 3.55 (d, J = 6.6
Hz, 2H), 6.36 (dt, J = 15.7, 6.6 Hz, 1H), 6.46 (d, J = 15.8 Hz, 1H),
7.17−7.26 (m, 4H), 7.27−7.33 (m, 4H), 7.34−7.37 (m, 2H). 13C
NMR (101 MHz, CDCl3): δ 39.3, 126.1, 126.2, 127.1, 128.47, 128.48,
128.7, 129.2, 131.1, 137.5, 140.2.
(E)-Ethyl 4-(3-(4-(Dimethylamino)phenyl)prop-1-enyl)benzoate
(14). Eluent: petroleum ether/EtOAc (60:1 v/v). Colorless oil, yield
0.127 g (82%). 1H NMR (400 MHz, CDCl3): δ 13C NMR (101 MHz,
CDCl3): δ 1.38 (t, J = 7.2 Hz, 3H), 2.92 (s, 6H), 3.47 (d, J = 5.2 Hz,
2H), 4.36 (q, J = 7.2 Hz, 2H), 6.41−6.52 (m, 2H), 6.72 (d, J = 8.8 Hz,
2H), 7.11 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.95 (d, J = 8.4
Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 14.3, 38.4, 40.8, 60.8, 113.0,
125.9, 127.4, 128.7, 129.3, 129.5, 129.8, 133.1, 142.1, 149.4, 166.5. HR-
MS: m/z 310.17966 [M + H]+; calcd for C20H24O2N, 310.18016.
(E)-4-(3-(4-Fluorophenyl)allyl)-N,N-dimethylaniline (15). Eluent:
petroleum ether/EtOAc (100:1 v/v). Colorless oil, yield 0.115 g
4-Cinnamyl-1,1′-biphenyl (6).24 Eluent: petroleum ether, yield
1
0.110 g (82%). H NMR (400 MHz, CDCl3): δ 3.56 (d, J = 6.6 Hz,
2H), 6.32−6.41 (m, 1H), 6.47 (d, J = 15.8 Hz, 1H), 7.15−7.22 (m,
1H), 7.24−7.44 (m, 9H), 7.50−7.60 (m, 4H). 13C NMR (101 MHz,
CDCl3): δ 38.9, 126.1, 127.0, 127.06, 127.11, 127.2, 128.5, 128.7,
129.0, 129.1, 131.2, 137.4, 139.1, 139.2, 141.0.
2-Cinnamylnaphthalene (7).24 Eluent: petroleum ether, yield
1
0.117 g (96%). H NMR (400 MHz, CDCl3): δ 3.71 (d, J = 6.2
Hz, 2H), 6.43 (dt, J = 15.8, 6.4 Hz, 1H), 6.51 (d, J = 15.9 Hz, 1H),
7.21 (t, J = 7.3 Hz, 1H), 7.30 (t, J = 7.5 Hz, 2H), 7.34−7.40 (m, 3H),
7.41−7.48 (m, 2H), 7.68 (s, 1H), 7.76−7.83 (m, 3H). 13C NMR (101
MHz, CDCl3): δ 39.5, 125.3, 126.0, 126.2, 126.7, 127.1, 127.4, 127.5,
127.6, 128.0, 128.5, 129.1, 131.3, 132.2, 133.7, 137.4, 137.6.
1
(90%). H NMR (400 MHz, CDCl3): δ 2.91 (s, 6H), 3.43 (d, J = 6.6
Hz, 2H), 6.25 (dt, J = 15.7, 6.6 Hz, 1H), 6.38 (d, J = 15.7 Hz, 1H),
6.71 (d, J = 8.7 Hz, 2H), 6.96 (t, J = 8.7 Hz, 2H), 7.10 (d, J = 8.7 Hz,
2H), 7.26−7.32 (m, 2H). 13C NMR (101 MHz, CDCl3): δ 38.3, 40.8,
113.0, 115.3 (d, J = 21.6 Hz), 127.5 (d, J = 7.9 Hz), 128.0, 129.1,
129.3, 130.0 (d, J = 2.1 Hz), 133.9 (d, J = 3.2 Hz), 149.3, 161.9 (d, J =
246.6 Hz). 19F NMR (376 MHz, CDCl3): δ −115.65. HR-MS: m/z
256.14943 [M + H]+; calcd for C17H19NF, 256.14960.
2-Cinnamyl-6-methoxynaphthalene (8). Eluent: petroleum ether/
EtOAc (100:1 v/v). White solid, yield 0.119 g (87%); mp 86−88 °C.
1H NMR (400 MHz, CDCl3): δ 3.66 (d, J = 6.2 Hz, 2H), 3.90 (s, 3H),
6.42 (dt, J = 15.8, 6.2 Hz, 1H), 6.49 (d, J = 15.9 Hz, 1H), 7.09−7.14
(m, 2H), 7.17−7.22 (m, 1H), 7.29 (t, J = 7.6 Hz, 2H), 7.32−7.39 (m,
3H), 7.60 (s, 1H), 7.68 (d, J = 8.4 Hz, 2H). 13C NMR (101 MHz,
CDCl3): δ 39.3, 55.3, 105.7, 118.7, 126.1, 126.6, 126.9, 127.1, 127.9,
128.5, 129.0, 129.1, 129.3, 131.1, 133.2, 135.3, 137.5, 157.3. HR-MS:
m/z 275.14306 [M + H]+; calcd for C20H19O, 275.14304.
(E)-N,N-Dimethyl-4-(3-(naphthalen-1-yl)allyl)aniline (16). Eluent:
petroleum ether/EtOAc (100:1 v/v). Colorless oil, yield 0.126 g
1
(88%). H NMR (400 MHz, CDCl3): δ 2.93 (s, 6H), 3.58 (d, J = 6.9
Hz, 2H), 6.37 (dt, J = 15.4, 6.9 Hz, 1H), 6.74 (d, J = 8.7 Hz, 2H),
7.13−7.20 (m, 3H), 7.41 (t, J = 7.8 Hz, 1H), 7.44−7.52 (m, 2H), 7.57
(d, J = 7.1 Hz, 1H), 7.73 (d, J = 8.2 Hz, 1H), 7.81−7.84 (m, 1H), 8.12
(d, J = 7.8 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 38.8, 40.9, 113.1,
123.6, 124.0, 125.59, 125.62, 125.8, 127.3, 127.6, 128.2, 128.4, 129.3,
131.2, 133.4, 133.6, 135.5, 149.4. HR-MS: m/z 288.17419 [M + H]+;
calcd for C21H22N, 288.17468.
(E)-N,N-Dimethyl-4-(3-(thiophen-2-yl)allyl)aniline (17). Eluent:
petroleum ether/EtOAc (60:1 v/v). Yellow oil, yield 0.102 g (84%).
1H NMR (400 MHz, CDCl3): δ 2.92 (s, 6H), 3.42 (d, J = 6.8 Hz, 2H),
6.19 (dt, J = 15.6, 6.8 Hz, 1H), 6.52 (d, J = 15.6 Hz, 1H), 6.71 (d, J =
8.7 Hz, 2H), 6.87 (d, J = 3.2 Hz, 1H), 6.90−6.94 (m, 1H), 7.08 (d, J =
5.2 Hz, 1H), 7.10 (d, J = 8.8 Hz, 2H). 13C NMR (101 MHz, CDCl3):
δ 38.1, 40.9, 113.0, 123.2, 123.5, 124.5, 127.2, 127.7, 129.3, 130.2,
142.9, 149.3. HR-MS: m/z 244.11487 [M + H]+; calcd for C15H18NS,
244.11545.
9-Cinnamylphenanthrene (9).25 Elute: petroleum ether, yield
1
0.137 g (93%). H NMR (400 MHz, CDCl3): δ 4.02 (d, J = 5.6
Hz, 2H), 6.50 (d, J = 16 Hz, 1H), 6.56 (dt, J = 15.9, 5.8 Hz, 1H),
7.15−7.21 (m, 1H), 7.27 (t, J = 7.5 Hz, 2H), 7.32−7.35 (m, 2H),
7.53−7.68 (m, 5H), 7.81−7.84 (m, 1H), 8.11−8.14 (m, 1H), 8.65 (d, J
= 8.1 Hz, 1H), 8.71−8.74 (m, 1H). 13C NMR (101 MHz, CDCl3): δ
36.7, 122.5, 123.2, 124.7, 126.1, 126.2, 126.3, 126.62, 126.64, 126.8,
127.1, 128.2, 128.48, 128.51, 129.9, 130.7, 131.3, 131.7, 131.9, 134.5,
137.4.
(E)-4-(3-(3-Methoxyphenyl)allyl)-N,N-dimethylaniline (10). Elu-
ent: petroleum ether/EtOAc (60:1 v/v). Colorless oil, yield 0.113 g
(85%). 1H NMR (400 MHz, CDCl3): δ 2.93 (s, 6H), 3.46 (d, J = 5.9
Hz, 2H), 3.80 (s, 3H), 6.29−6.45 (m, 2H), 6.70−6.78 (m, 3H), 6.90
(s, 1H), 6.95 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 8.4 Hz, 2H), 7.20 (t, J =
7.9 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 38.3, 40.9, 55.2, 111.2,
F
DOI: 10.1021/acs.joc.5b02151
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The Journal of Organic Chemistry
Note
(E)-4-(3-(4-Chlorophenyl)allyl)-N,N-dimethylaniline (18). Eluent:
petroleum ether/EtOAc (100:1 v/v). Colorless oil, yield 0.236 g (1.5
mmol scale, 58%). 1H NMR (400 MHz, CDCl3): δ 2.92 (s, 6H), 3.44
(d, J = 5.5 Hz, 2H), 6.26−6.39 (m, 2H), 6.72 (d, J = 8.6 Hz, 2H), 7.10
(d, J = 8.6 Hz, 2H), 7.22−7.28 (m, 4H). 13C NMR (101 MHz,
CDCl3): δ 38.3, 40.9, 113.0, 127.3, 127.8, 128.5, 129.1, 129.3, 131.0,
132.4, 136.2, 149.3. HR-MS: m/z 272.12000, 274.11694 [M + H]+;
calcd for C17H19N35Cl 272.12005, C17H19N37Cl 274.11710.
7.47−7.52 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 21.1, 38.4, 40.9,
113.1, 126.4, 126.7, 126.9, 128.2, 129.3, 129.4, 129.9, 130.2, 136.5,
136.9, 138.0, 139.6, 149.3. HR-MS: m/z 328.20599 [M + H]+; calcd
for C24H26N, 328.20598.
ASSOCIATED CONTENT
■
S
* Supporting Information
(E)-4′-(3-(4-(Dimethylamino)phenyl)prop-1-en-1-yl)-N,N-dimeth-
yl-[1,1′-biphenyl]-4-amine (19). Eluent: petroleum ether/EtOAc
(50:1 v/v). White solid, yield 0.059 g (1.5 mmol scale, 11%); mp
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.5b02151.
1
Table on catalyst evaluation and optimization of reaction
conditions and copies of NMR spectra of allyl methyl
ethers and the cross-coupling products (PDF)
147 °C. H NMR (400 MHz, CDCl3): δ 2.92 (s, 6H), 2.98 (s, 6H),
3.47 (d, J = 6.5 Hz, 2H), 6.35 (dt, J = 15.7, 6.6 Hz, 1H), 6.45 (d, J =
15.8 Hz, 1H), 6.72 (d, J = 8.8 Hz, 2H), 6.79 (d, J = 8.9 Hz, 2H), 7.13
(d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.47−7.52 (m, 4H). 13C
NMR (101 MHz, CDCl3): δ 38.4, 40.6, 40.9, 112.8, 113.1, 126.2,
126.4, 127.4, 128.3, 128.9, 129.3, 129.5, 130.1, 135.5, 139.7, 149.3,
149.9. HR-MS: m/z 357.23239 [M + H]+; calcd for C25H29N2,
357.23253.
AUTHOR INFORMATION
■
Corresponding Author
(E)-N,N-Dimethyl-4-(4-phenylbut-3-en-2-yl)aniline (20).21 Eluent:
*E-mail: zxwang@ustc.edu.cn.
1
petroleum ether/EtOAc (100:1 v/v), yield 0.114 g (91%). H NMR
Notes
(400 MHz, CDCl3): δ 1.43 (d, J = 7.0 Hz, 3H), 2.92 (s, 6H), 3.51−
3.60 (m, 1H), 6.36−6.39 (m, 2H), 6.72 (d, J = 8.8 Hz, 2H), 7.15 (d, J
= 8.5 Hz, 2H), 7.18 (d, J = 7.3 Hz, 1H), 7.27 (t, J = 7.6 Hz, 2H),
7.33−7.36 (m, 2H). 13C NMR (101 MHz, CDCl3): δ 21.2, 40.8, 41.5,
112.9, 126.1, 126.8, 127.83, 127.86, 128.4, 133.6, 136.1, 137.8, 149.3.
(E)-N,N-Dimethyl-4-(1-phenylpent-1-en-3-yl)aniline (21). Eluent:
petroleum ether/EtOAc (100:1 v/v). Colorless oil, yield 0.121 g
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Natural Science
Foundation of China (Grant 21172208) and the National
Basic Research Program of China (Grant 2015CB856600) is
gratefully acknowledged. Ms. Wen-Jing Pan and Ms. Fang He
of the Department of Chemistry, University of Science and
Technology of China, are thanked for their help with sample
purification.
1
(91%). H NMR (400 MHz, CDCl3): δ 0.91 (t, J = 7.4 Hz, 3H),
1.74−1.84 (m, 2H), 2.92 (s, 6H), 3.22 (q, J = 7.2 Hz, 1H), 6.31 (dd, J
= 15.8, 7.0 Hz, 1H), 6.37 (d, J = 15.9 Hz, 1H), 6.72 (d, J = 8.7 Hz,
2H), 7.12 (d, J = 8.7 Hz, 2H), 7.17 (t, J = 7.2 Hz, 1H), 7.26 (t, J = 7.6
Hz, 2H), 7.34 (d, J = 7.2 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ
12.3, 28.7, 40.8, 49.9, 112.9, 126.1, 126.8, 128.2, 128.4, 128.8, 132.5,
135.0, 137.9, 149.2. HR-MS: m/z 266.19022 [M + H]+; calcd for
C19H24N, 266.19033.
REFERENCES
■
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1
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1
0.112 g (80%). H NMR (400 MHz, CDCl3): δ 0.82 (d, J = 6.6 Hz,
3H), 0.98 (d, J = 6.6 Hz, 3H), 1.95−2.05 (m, 1H), 2.92 (s, 6H), 2.94−
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= 8.8 Hz, 2H), 7.23 (d, J = 7.8 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H),
G
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