Nickel-Catalyzed Benzylation of Aryl Alkenes with Benzylamines via C-N Bond Activation

Article abstract of DOI:10.1021/acs.joc.8b02279

We have developed the first example of nickel-catalyzed Heck-type benzylation of aryl olefins with various benzylamines as benzyl electrophiles, and the benzylic C-N bond cleavage was efficiently promoted by the amine-I₂ charge transfer complex (CT complex). The combination of low-cost NiCl₂ and I₂ has been found to facilitate Heck reaction of tertiary benzylamines and alkenes into various benzyl-substituted alkenes in good to excellent yields. This unconventional Heck reaction is proposed to go through initially the formation of a benzylic radical via oxidative addition of the C-N bond with Ni(0), then capturing by aryl alkene via radical addition, followed by single-electron transfer redox and proton abstraction without oxidant and external base.

Full text of DOI:10.1021/acs.joc.8b02279

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Article
Nickel-Catalyzed Benzylation of Aryl Alkenes
with Benzylamines via C-N Bond Activation
Hui Yu, Bin Hu, and Hanmin Huang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02279 • Publication Date (Web): 29 Oct 2018
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Nickel-Catalyzed Benzylation of Aryl Alkenes with Benzylamines via
C-N Bond Activation
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Hui Yu,†,§ Bin Hu,*,† and Hanmin Huang*,†,‡
†State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy
of Sciences, Lanzhou, 730000, P. R. China
‡Hefei National Laboratory for Physical Sciences at the Microscale, and Department of Chemistry, Center for Excellence in
Molecular Synthesis, University of Science and Technology of China, Chinese Academy of Sciences, Hefei, 230026, P. R.
China
§University of Chinese Academy of Sciences, Beijing, 100049, P. R. China
ABSTRACT: We have developed the first example of nickel-catalyzed Heck-type benzylation of aryl olefins with various
benzylamines as benzyl electrophiles, and the benzylic C-N bond cleavage was efficiently promoted by amine-I2 charge transfer
complex (CT-complex). The combination of low-cost NiCl2 and I2 has been found to facilitate Heck reaction of tertiary
benzylamines and alkenes into various benzyl-substituted alkenes in good to excellent yields. This unconventional Heck reaction is
proposed to go through initially the formation of a benzylic radical via oxidative addition of C-N bond with Ni(0), then captured by
aryl alkene via radical addition, followed by single-electron transfer redox and proton abstraction without oxidant and external base.
Compared with benzyl halides, to the best of our knowledge,
no simple amine has been directly used as electrophile precur-
INTRODUCTION
The Heck reaction has become one of the most powerful strat-
sors in Heck reaction, which is in largely due to the deficiency
egies for the construction of C-C bonds since its discovery in
of effective strategies for cleavage of inert C-N bonds.
Scheme 1. Classic and Unexplored Benzyl Electrophiles in
the Heck reaction.
1972.1 The classic Heck reaction delivers functionalized al-
kenes that are essential structural motifs for the synthesis of
pharmaceuticals, organic materials, agrochemicals, and com-
plex natural products in both academic and industrial settings.2
Although tremendous effort has been devoted to the develop-
ment of this synthetically useful reaction, compared with sig-
nificant advances on the field of alkyl halides, vinyl or aryl
halides cross coupling,3 comparatively little progress has been
achieved in the Heck reaction of non-halogen-containing alkyl
electrophiles such as amines.
As one of the most ample chemical bonds, C-N bond exists
widespreadly in organic molecules and bioactive molecules.4
On account of the high C-N bond dissociation energy and
Our group has recently been focusing on developing effi-
good nucleophilicity of the amine group, amines are more
cient strategies for activation of inert C-N bond of simple
commonly acted as nucleophiles in organic transformations.
amines merging transition-metal catalysis. Several useful
As for utilizing as Heck-reaction coupling partners, amines
strategies have been developed and successfully employed in a
were usually transformed into the corresponding energetically
series of C-C and C-N bond construction reactions.9,10 The key
to the success of those competent strategies is to enhance the
oxidation state of the amines by lowering the electron-density
of the nitrogen atom. Such kind of strategies could not only
facilitate the C-N bond to form σ-complex with a transition
metal, but also improve the π-back bonding capability between
metal center and C-N bond, and ultimately realize C-N bond
activation by oxidative addition with low valence transition
metal. One strategy with great promise for amine-I2 CT-
favored compounds such as diazonium salts,5,6 or ammonium
salts.7 Such kind of strategies usually produce lots of wastes,
thus, cannot fit for the idea of sustainable development. Heck-
type benzylation of alkenes is a useful method for synthesis of
allylic compounds. The traditional benzyl electrophiles for
such a reaction were toxic benzyl halides or related deriva-
tives,8 delivering two kinds of products (Internal and Terminal
products) according to the property of olefins, and limiting the
development of alkene benzylation reaction (Scheme 1A).
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complex promoted benzylic C-N bond activation has been
impact of various phosphine ligands was then screened with
low-cost NiCl2 as the ideal catalyst, and the corresponding
Table 2. Substrate Scope of Benzylamines a
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realized and applied in the nickel-catalyzed direct carbonyla-
tion of benzylamines and alkylarylation of activated alkenes
successfully.10 Mechanistic studies have disclosed that the
formation of amine-I2 complex leads to reinforcement of π-
back bonding capability between metal center and C-N bond,
thus prompts C-N bond experiencing single electron oxidative
addition with Ni0 to deliver a benzylic radical without external
oxidant. In this context, it would be reasonable that benzylic
radicals generated from the benzylamines by CT-complex
induced C-N bond cleavage could be applied to nickel cata-
lyzed Heck-type benzylation reaction. Herein, we develop a
nickel-catalyzed Heck-type benzylation reaction of aryl al-
kenes with benzylamines as benzyl electrophile precursors in
the absence of external bases via C-N bond activation
(Scheme 1B).
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RESULTS AND DISCUSSION
Our initial effort was made to achieve the successful cross
coupling of readily available N-benzyl-N-isopropylpropan-2-
amine (1a) and 1,1-diphenylethylene (2a) (Table 1). After
Table 1. Screening of Reaction Conditions a
entry
1
[Ni]
ligand
solvent
anisole
anisole
anisole
anisole
anisole
anisole
anisole
anisole
CH3CN
DMF
yield (%)
47
NiCl2
NiBr2
NiI2
Xantphos
Xantphos
Xantphos
Xantphos
PCy3
2
45
3
45
4
Ni(cod)2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
-
40
5
25
6
DPPF
32
7
DPPOct
31
8
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
Cy-Xantphos
-
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9
6
10
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12
13b
14c
15b
16b
22
DME
15
toluene
anisole
anisole
anisole
anisole
23
93(90)
0
17
NiCl2
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aReaction conditions: 1a (1.0 mmol), 2a (0.5 mmol), [Ni] (0.025
mmol), ligand (monodentate ligand : 0.06 mmol; bidentate ligand :
0.03 mmol), I2 (0.1 mmol), solvent (2 mL), 150 oC, 16 h. GC
yield determined by using n-dodecane as an internal standard and
isolated yields were given within parentheses; bI2 (0.2 mmol);
cWithout I2.
aReaction conditions: 1 (1.0 mmol), 2a (0.5 mmol), NiCl2 (0.025
mmol), Cy-Xantphos (0.03 mmol), I2 (0.2 mmol), anisole (2 mL),
150 oC, 16 h. bIsolated yield.
extensive and systematic study, gratifyingly, the cross-coupled
o
adduct 3aa was obtained in 47% GC yield at 150 C when
results indicated that the commercialized Cy-Xantphos was
the best ligand for Heck reaction to deliver the benzylated
alkene 3aa in 54% GC yield (Table 1, entry 8). As shown in
entries 9-12, some common organic solvents such as CH3CN,
DMF, DME and toluene were also evaluated, however, they
afforded unsatisfying yields of 3aa. To our great delight, fur-
ther increasing the catalyst loading of I2 to 40 mol%, the ben-
zylated adduct 3aa was isolated in 90% yield under other iden-
simple catalytic system NiCl2/Xantphos was combined with
catalytic amount of I2 (Table 1, entry 1). Further screening of
other representative nickel catalysts proved that both Ni(0) and
Ni(II) could catalyze this Heck reaction to produce 3aa and
various nickel precursor did not greatly influence the trans-
formation (Table 1, entries 2-4). Inspired by this positive lead,
we next sought to improve the efficiency of the reaction. The
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tical reaction conditions (Table 1, entry 13). As we expected,
was dramatically decreased under the same reaction conditions.
The relatively higher activity of the substrate with isopropyl
(i-Pr) might be attributed to the combined effect of electrical
property and steric hindrance. Taking the significantly differ-
ent reactivity of benzylamines with diverse substituents into
consideration, we focused our attention on the various benzyl-
amines with leaving group -N(i-Pr)2 to study its substrate
scope and generality, and the results are summarized in Table
2. Various benzylamines bearing different functional groups
such as alkyl and halogen on the phenyl ring can be applied to
this unconventional Heck reaction, affording different ben-
zylated adducts 3ba-3ma in 64-95% yields (Table 2, entries
11-22). Apart from common benzyl-substituted amines, as
shown in entries 23 and 24, naphthyl substituted amines were
also applicable to this transformation, delivering the benzylat-
ed alkenes 3na and 3oa in excellent yields. We were also glad
to see that 2-thienyl-substituted amine 1p is also compatible
with this Heck reaction and proceed efficiently to afford the
benzylated alkenes 3pa in 86% isolated yield (Table 2, entry
25). Moreover, benzylamines with α-substituted group 1q and
1r were also applicable to this transformation, providing cor-
responding adducts 3qa and 3ra in 76% and 73% yield, re-
spectively (Table 2, entries 26 and 27).
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8
control experiments demonstrated that no desired adduct could
be detected when the Heck reaction was dealt without I2 and
adduct 3aa was isolated in only 17% yield under metal-free
conditions, in addition, some additives such as AcOH and
MeOTf instead of iodine were not effective for this transfor-
mation (See the Supporting Information), and the above re-
sults indicated iodine and nickel catalyst are crucial for the
Heck reaction to proceed smoothly (Table 1, entries 14 and
15). While this reaction was conducted in the absence of Cy-
Xantphos, the desired adduct 3aa was still isolated in 57%
yield (Table 1, entry 16), which revealed that the ligand is not
necessary for this Heck-type benzylation.
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Scheme 2. Substrate Scope of alkenes a,b
Scheme 3. Deuterium-Labeled Experiments
Next, the scope of aryl alkenes 2 was investigated under the
optimal reaction conditions. As shown in Scheme 2, both elec-
tron donating group and electron withdrawing group on the
phenyl ring of symmetrical diarylalkenes were well tolerated,
providing the cross-coupling products 3ab-3af in 67-92%
isolated yields. In addition to symmetrical arenes, asymmet-
rical diarylalkenes were also compatible with this transfor-
mation, generating the corresponding mixed adducts 3ag-3ak
in 82-92% isolated yields but lower selectivity, which may
partly attribute to high reaction temperature. Furthermore, α-
methyl substituted styrene 2l-2r underwent the benzylation
reaction in moderate yields, affording the corresponding prod-
ucts as a mixture of terminal and internal according to the
different position of carbon-carbon double bond. It is worth
noting that when α-tert-butyl styrene 2s was submitted to this
Heck reaction, the adduct 3as was obtained in 50% isolated
yield and with excellent Z-selectivity because of steric hin-
drance. Unfortunately, only low yields but good E-selectivity
were obtained for the 4-fluorostyrene 2t and 4-isobutylstyrene
2u, besides, other types of alkenes such as acrylate are not
compatible with this transformation (For more details see the
Supporting Information).
aReaction conditions: 1a (1.0 mmol), 2 (0.5 mmol), NiCl2 (0.025
mmol), Cy-Xantphos (0.03 mmol), I2 (0.2 mmol), anisole (2 mL),
150 oC, 16 h. bIsolated yield, the ratio of Z/E and T/I (termi-
nal/internal) was determined by GC-MS analysis of the crude
product.
After establishing the optimum reaction conditions, we next
examined the substrate scope of benzylamines. Considering
different substituents linked to nitrogen atom may have a re-
markable influence on the reactivity, benzylic amines with
different leaving groups (NR'2) were firstly screened under
optimized reaction conditions. As we expected, the substrates
with different substituents R' on the N atom delivered the de-
sired cross-coupled product 3aa in distinctly different yields
(Table 2, entries 1-10). When the substrates with different
leaving groups, such as -N(i-Pr)2, -NCy2 and -NBn2 were con-
ducted in this reaction, the desired alkene 3aa was obtained in
77-90% yields under the optimal reaction conditions (Table 2,
entries 5, 9 and 10). For the benzylamines with H, methyl
(Me), ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu), allyl and
phenyl (Ph) as substituents, however, the yield of product 3aa
To gain some mechanistic insights into the reaction pathway,
a few control experiments were carried out. It is found that the
desired adduct 3aa could not be detected in the presence of
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radical scavenger TEMPO (see the supporting information),
Page 4 of 8
0.5 mmol), I2 (50.8 mg, 0.2 mmol) and anisole (2 mL) was
added to a 25 mL flame-dried Young-type tube under argon
atmosphere. The mixture was stirred at 150oC for 16 hours.
After the reaction finished, the solvent was removed under
reduced pressure and the residue was purified by flash column
chromatography on silica gel and eluted with ethyl
acetate/petroleum ether (1/200-1/50) to afford the desired
product 3aa.
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which indicates that a radical pathway proceeding through a
single-electron transfer process is highly possible in this trans-
formation. In addition, when 2a-d2 instead of 2a was added
into this system, the benzylated alkene 3aa-d was isolated in
82% yield with 88% D (Scheme 3a). The result KH/KD = 1.1 of
an intermolecular competition KIE experiment indicates that
C-H bond cleavage is not involved in the rate-determining step
of the Heck-type benzylation process (Scheme 3b).
Spectroscopic Data of the Products. Prop-1-ene-1,1,3-
On the basis of our previous work10and mechanistic studies,
the most plausible mechanism is illustrated in Figure 1. Initial-
ly, an active Ni(0) center which may be generated by the re-
duction of Ni(II) with phosphine ligand or benzylamine un-
derwent oxidative addition with the amine-I2 CT complex A to
form the benzylic radical B, then this radical could be captured
by the alkene through radical addition process to deliver the
radical intermediate C, followed by the reduction of NiI to Ni0
with intermediate C via single-electron transfer (SET). In the
same time, the proton included in the oxidized intermediate C
was removed by the inner base R'2N- to afford the desired
product 3 with the release of R'2NH.
triyltribenzene (3aa). Colorless oil (122 mg, 90 % yield). H
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NMR (400 MHz, CDCl3) δ 7.17-7.40 (m, 15H), 6.27 (t, J =
7.6 Hz, 1H), 3.46 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100
MHz, CDCl3) δ 142.6, 142.6, 141.1, 139.9, 130.1, 128.6,
128.5, 128.4, 128.2, 127.9, 127.5, 127.3, 127.2, 126.1, 36.1;
HRMS (ESI) calcd. for C21H17 [M-H]﹣ : 269.1335, found:
269.1317.
(3-(o-Tolyl)prop-1-ene-1,1-diyl)dibenzene (3ba). Colorless
oil (135 mg, 95 % yield). 1H NMR (400 MHz, CDCl3) δ 7.29-
7.40 (m, 3H), 7.11-7.25 (m, 11H), 6.19 (t, J = 7.2 Hz, 1H),
3.42 (d, J = 7.6 Hz, 2H ), 2.18 (s, 3H); 13C NMR {1H} (100
MHz, CDCl3) δ 142.6, 140.0, 139.4, 136.4, 130.2, 130.0,
128.8, 128.4, 128.2, 127.5, 127.3, 127.2, 126.3, 126.2, 33.9,
19.6; HRMS (ESI) calcd. for C22H19 [M-H]﹣: 283.1491, found:
283.1472.
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Figure 1. Plausible Reaction Mechanism
(3-(m-Tolyl)prop-1-ene-1,1-diyl)dibenzene (3ca). Colorless
oil (122 mg, 86 % yield). 1H NMR (400 MHz, CDCl3) δ 7.29-
7.40 (m, 3H), 7.15-7.25 (m, 8H), 6.98-7.01 (m, 3H), 6.26 (t, J
= 7.6 Hz, 1H), 3.42 (d, J = 7.6 Hz, 2H), 2.32 (s, 3H); 13C NMR
{1H} (100 MHz, CDCl3) δ 142.6, 142.5, 141.0, 140.0, 138.2,
130.1, 129.3, 128.5. 128.4, 128.2, 128.0, 127.5, 127.2, 127.2,
126.9, 125.6, 36.0, 21.6; HRMS (ESI) calcd. for C22H19 [M-H]
﹣: 283.1491, found: 283.1473.
(3-(p-Tolyl)prop-1-ene-1,1-diyl)dibenzene (3da). Colorless
oil (128 mg, 90 % yield). 1H NMR (400 MHz, CDCl3) δ 7.26-
7.39 (m, 3H), 7.16-7.24 (m, 7H), 7.06-7.11 (m, 4H), 6.25 (t, J
= 7.6 Hz, 1H), 3.42 (d, J = 7.6 Hz, 2H), 2.31 (s, 3H); 13C NMR
{1H} (100 MHz, CDCl3) δ 142.6, 142.4, 140.0, 138.0, 135.6,
130.1, 129.3, 128.4, 128.2, 128.2, 127.5, 127.2, 127.1, 35.6,
21.1; HRMS (ESI) calcd. for C22H19 [M-H]﹣: 283.1491, found:
283.1472.
CONCLUSION
In summary, we have described a novel nickel-catalyzed
Heck type benzylation of aryl alkenes with benzylamines via
benzylic C-N bond cleavage, in which the cheap and easily
accessible benzylamines were used as benzyl electrophile.
Compared with traditional benzyl electrophiles, our reaction
avoids the use of base and toxic benzyl halides, providing a
practical and efficient approach to obtain various benzylated
alkenes. Further application of this strategy is in progress.
(3-(2-Chlorophenyl)prop-1-ene-1,1-diyl)dibenzene
(3ea).
Colorless oil (116 mg, 76 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.29-7.40 (m, 4H), 7.10-7.25 (m, 10H), 6.23 (t, J =
7.6 Hz, 1H), 3.55 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100
MHz, CDCl3) δ 143.4, 142.5, 139.8, 138.7, 134.1, 130.3,
130.0, 129.6, 128.5, 128.3, 127.6, 127.5, 127.4, 127.3, 127.0,
126.1, 33.9; HRMS (ESI) calcd. for C21H17ClNa [M+Na]﹢:
327.0911, found: 327.0906.
EXPERIMENTAL SECTION
General Information. All non-aqueous reactions and
manipulations were operated under argon atmosphere. All
solvents were dried and distilled before use. TLC was
performed on a silica gel-coated plates. NMR spectra were
recorded on BRUKER Avence III 400 MHz spectrometers
(3-(3-Chlorophenyl)prop-1-ene-1,1-diyl)dibenzene
(3fa).
Colorless oil (100 mg, 66 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.30-7.40 (m, 3H), 7.14-7.28 (m, 10H), 7.04-7.06 (m,
1H), 6.21 (t, J = 8.0 Hz, 1H), 3.42 (d, J = 7.6 Hz, 2H); 13C
NMR {1H} (100 MHz, CDCl3) δ 143.3, 143.1, 142.3, 139.7,
134.4, 130.0, 129.8, 128.6, 128.5, 128.3, 127.5, 127.4, 127.4,
126.7, 126.7, 126.3, 35.7; HRMS (ESI) calcd. for C21H17ClNa
[M+Na]﹢: 327.0911, found: 327.0908.
1
(400 MHz for H NMR, 100 MHz for 13C{1H} NMR and 376
MHz for 19F NMR). Chemical shifts were expressed in parts
per million (ppm), and coupling constants (J) given in Hz.
High resolution mass spectra (HRMS) were performed using
ESI or EI. GC analysis were performed on Agilent 7890 with
OV-225 column or Hp-5 column, and GS-MS analysis
performed with Agilent 7890A/5975C GC-MS system. All of
the benzylamines and alkenes are known compounds and
synthesized according to the reported methods.11
(3-(4-Chlorophenyl)prop-1-ene-1,1-diyl)dibenzene (3ga).
Colorless oil (126 mg, 83 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.29-7.40 (m, 3H), 7.20-7.27 (m, 9H), 7.08-7.11 (m,
2H), 6.20 (t, J = 7.6 Hz, 1H), 3.41 (d, J = 7.6 Hz, 2H); 13C
NMR {1H} (100 MHz, CDCl3) δ 143.1, 142.3, 139.8, 139.5,
131.9, 130.0, 129.8, 128.7, 128.5, 128.3, 127.5, 127.4, 127.3,
General Procedure. A mixture of NiCl2 (3.2 mg, 0.025
mmol), Cy-Xantphos (18.1 mg, 0.03 mmol), N,N-
diisopropylbenzylamine (1a) (191 mg, 1.0 mmol), 2a (90 mg,
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127.1, 35.4; HRMS (ESI) calcd. for C21H17ClNa [M+Na]﹢:
327.0911, found: 327.0910.
2-(3,3-Diphenylallyl)naphthalene (3oa). Colorless oil (141
mg, 88 % yield). 1H NMR (400 MHz, Acetone-d6) δ 7.81-7.85
(m, 3H), 7.70 (s, 1H), 7.35-7.48 (m, 6H), 7.21-7.31 (m, 7H),
6.40 (t, J = 7.6 Hz, 1H), 3.60 (d, J = 7.6 Hz, 2H); 13C NMR
{1H} (100 MHz, Acetone-d6) δ 143.6, 143.3, 140.8, 139.4,
134.8, 133.2, 130.7, 129.3, 129.1, 129.0, 128.5, 128.4, 128.4,
128.2, 128.1, 128.1, 128.0, 127.1, 126.9, 126.2, 36.7; HRMS
(ESI) calcd. for C25H19 [M-H]﹣: 319.1491, found: 319.1467.
2-(3,3-Diphenylallyl)thiophene (3pa). Colorless oil (119 mg,
86 % yield). 1H NMR (400 MHz, Acetone-d6) δ 7.41-7.45 (m,
2H), 7.34-7.38 (m, 1H), 7.21-7.31 (m, 8H), 6.93-6.95 (m, 1H),
6.86-6.87 (m, 1H), 6.31 (t, J = 7.6 Hz, 1H), 3.61 (dd, J1 = 0.8
Hz, J2 = 7.6 Hz, 2H); 13C NMR {1H} (100 MHz, Acetone-d6) δ
144.3, 143.6, 143.1, 140.4, 130.6, 129.3, 129.1, 128.3, 128.2,
128.1, 127.8, 127.6, 125.3, 124.5, 30.8; HRMS (ESI) Calcd
for C19H16NaS [M+Na]﹢: 299.0865, Found: 299.0868.
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(3-(2,6-Dichlorophenyl)prop-1-ene-1,1-diyl)dibenzene
(3ha). Colorless oil (159 mg, 94 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.17-7.43 (m, 12H), 7.03-7.07 (m, 1H), 5.97 (t, J =
6.8 Hz, 1H), 3.76 (d, J = 6.8 Hz, 2H); 13C NMR {1H} (100
MHz, CDCl3) δ 143.4, 142.4, 140.0, 136.9, 135.7, 130.1,
128.3, 128.3, 128.2, 128.0, 127.5, 127.3, 127.2, 124.6, 32.3;
HRMS (ESI) calcd. for C21H17Cl2 [M+H]﹢: 339.0702, found:
339.0697.
9
(3-(4-Fluorophenyl)prop-1-ene-1,1-diyl)dibenzene
(3ia).
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Colorless oil (105 mg, 73 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.19-7.40 (m, 10H), 7.11-7.14 (m, 2H), 6.93-6.99 (m,
2H), 6.22 (t, J = 7.6 Hz, 1H), 3.42 (d, J = 7.6 Hz, 2H); 13C
NMR {1H} (100 MHz, CDCl3) δ 160.3 (d, J = 242.4 Hz),
142.8, 142.4, 139.8, 136.7 (d, J = 3.1 Hz), 130.0, 129.8 (d, J =
7.9 Hz), 128.5, 128.3, 127.6, 127.5, 127.4, 127.3, 115.2 (d, J =
21.1 Hz), 35.2; 19F NMR (376 MHz CDCl3) δ -117.3; HRMS
(ESI) calcd. for C21H17FNa [M+Na] ﹢ : 311.1206, found:
311.1196.
But-1-ene-1,1,3-triyltribenzene (3qa). Colorless oil (108 mg,
1
76 % yield). H NMR (400 MHz, CDCl3) δ 7.15-7.39 (m,
15H), 6.20 (d, J = 10.4 Hz, 1H), 3.56-3.64 (m, 1H), 1.37 (d, J
= 6.8 Hz, 3H); 13C NMR {1H} (100 MHz, CDCl3) δ 146.3,
142.5, 140.3, 140.2, 134.3, 129.9, 128.6, 128.4, 128.2, 127.4,
127.2, 127.1, 127.1, 126.1, 39.4, 22.5; HRMS (ESI) calcd. for
C22H19 [M-H]﹣: 283.1491, found: 283.1469.
4-(3,3-Diphenylallyl)benzonitrile (3ja). Colorless oil (112
mg, 76 % yield). 1H NMR (400 MHz, CDCl3) δ 7.46-7.48 (m,
2H), 7.22-7.32 (m, 3H), 7.09-7.19 (m, 9H), 6.10 (t, J = 7.6 Hz,
1H), 3.41 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100 MHz,
CDCl3) δ 146.7, 144.0, 142.0, 139.5, 132.4, 129.8, 129.2,
128.5, 128.3, 127.5, 127.4, 125.6, 119.1, 110.0, 36.1; HRMS
(ESI) calcd. for C22H17NNa [M+Na] ﹢ : 318.1253, found:
318.1247.
(3-(4-Methoxyphenyl)prop-1-ene-1,1-diyl)dibenzene (3ka).
Colorless oil (141 mg, 94 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.29-7.39 (m, 3H), 7.18-7.25 (m, 7H), 7.09-7.11 (m,
2H), 6.81-6.85 (m, 2H), 6.24 (t, J = 7.6 Hz, 1H), 3.76 (s, 3H),
3.39 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100 MHz, CDCl3) δ
158.1, 142.6, 142.3, 140.0, 133.1, 130.1, 129.4, 128.4, 128.3,
128.2, 127.5, 127.2, 127.1, 114.0, 55.4, 35.2; HRMS (EI)
calcd. for C22H20O [M]+: 300.1509, found: 300.1505.
Prop-1-ene-1,1,3,3-tetrayltetrabenzene (3ra). Colorless oil
1
(126 mg, 73 % yield). H NMR (400 MHz, CDCl3) δ 7.14-
7.38 (m, 20H), 6.53 (d, J = 10.4 Hz, 1H), 4.80 (d, J = 10.8 Hz,
1H); 13C NMR {1H} (100 MHz, CDCl3) δ 144.6, 142.4, 141.7,
139.8, 131.1, 129.9, 128.6, 128.5, 128.4, 128.3, 127.6, 127.4,
127.4, 126.4, 50.7; HRMS (EI) calcd. for C27H22 [M]+:
346.1717; found: 346.1713.
4,4'-(3-Phenylprop-1-ene-1,1-diyl)bis(methylbenzene) (3ab).
Colorless oil (131mg, 88 % yield). 1H NMR (400 MHz, CDCl3)
δ 7.26-7.30 (m, 2H), 7.11-7.20 (m, 9H), 7.04 (d, J = 8.0 Hz,
2H), 6.19 (t, J = 7.6 Hz, 1H), 3.46 (d, J = 7.6 Hz, 2H), 2.37 (s,
3H), 2.31 (s, 3H); 13C NMR {1H} (100 MHz, CDCl3) δ 142.4,
141.3, 140.0, 137.1, 136.9, 136.8, 130.0, 129.1, 128.9, 128.6,
128.6, 127.4, 126.8, 126.0, 36.1, 21.4, 21.2; HRMS (ESI)
calcd. for C23H21 [M-H]﹣: 297.1648, found: 297.1625.
4,4'-(3-Phenylprop-1-ene-1,1-diyl)bis(fluorobenzene) (3ac).
Colorless oil (141 mg, 92 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.27-7.31 (m, 2H), 7.16-7.22 (m, 7H), 7.05-7.10 (m,
2H), 6.92-6.97 (m, 2H), 6.20 (t, J = 7.6 Hz, 1H), 3.43 (d, J =
7.6 Hz, 2H); 13C NMR {1H} (100 MHz, CDCl3) δ 161.1 (d, J
= 245.2 Hz), 161.0 (d, J = 244.9 Hz), 140.8, 140.6, 138.6 (d, J
= 3.2 Hz), 135.6 (d, J = 3.5 Hz), 131.6 (d, J = 7.9 Hz), 129.0
(d, J = 7.8 Hz), 128.7, 128.5, 128.1, 126.3, 115.4 (d, J = 21.2
Hz), 115.0 (d, J = 21.2 Hz), 36.0; 19F NMR (376 MHz CDCl3)
δ -114.7, -115.3; HRMS (EI) calcd. for C21H16F2 [M]+:
306.1215; Found: 306.1217.
4,4'-(3-Phenylprop-1-ene-1,1-diyl)bis(chlorobenzene) (3ad).
Colorless oil (140 mg, 83 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.34-7.37 (m, 2H), 7.27-7.31 (m, 2H), 7.11-7.23 (m,
9H), 6.24 (t, J = 7.6 Hz, 1H), 3.43 (d, J = 7.6 Hz, 2H); 13C
NMR {1H} (100 MHz, CDCl3) δ 140.6, 140.5, 140.4, 137.8,
133.5, 133.3, 131.4, 129.0, 128.8, 128.7, 128.7, 128.5, 128.4,
126.3, 36.0; HRMS (EI) Calcd for C21H16Cl2 [M]+: 338.0624,
Found: 338.0626.
1-(4-(3,3-Diphenylallyl)phenyl)ethanone (3la). Colorless oil
1
(125 mg, 80 % yield). H NMR (400 MHz, CDCl3) δ 7.88-
7.90 (m, 2H), 7.31-7.41 (m, 3H), 7.20-7.28 (m, 9H), 6.23 (t, J
= 7.6 Hz, 1H), 3.51 (d, J = 7.6 Hz, 2H), 2.57 (s, 3H),; 13C
NMR {1H} (100 MHz, CDCl3) δ 197.9, 146.8, 143.5, 142.2,
139.6, 135.3, 129.9, 128.8, 128.7, 128.5, 128.3, 127.4, 127.4,
126.4, 36.0, 26.7; HRMS (ESI) Calcd for C23H20NaO [M+Na]
﹢: 335.1406, Found:335.1395.
Methyl 4-(3,3-Diphenylallyl)benzoate (3ma). Colorless oil
1
(105 mg, 64 % yield). H NMR (400 MHz, CDCl3) δ 7.95-
7.97 (m, 2H), 7.30-7.40 (m, 3H), 7.20-7.28 (m, 9H), 6.24 (t, J
= 7.6 Hz, 1H), 3.89 (s, 3H), 3.50 (d, J = 7.6 Hz, 2H); 13C NMR
{1H} (100 MHz, CDCl3) δ 167.2, 146.6, 143.4, 142.3, 139.7,
129.9, 129.9, 128.5, 128.5, 128.3,128.1, 127.4, 127.4, 127.4,
126.6, 52.1, 36.1; HRMS (ESI) calcd. for C23H20NaO2 [M+Na]
﹢: 351.1356, found: 351.1349.
1-(3,3-Diphenylallyl)naphthalene (3na). Colorless oil (149
mg, 93 % yield). 1H NMR (400 MHz, Acetone-d6) δ 7.87-7.92
(m, 2H), 7.75-7.77 (m, 1H), 7.30-7.49 (m, 9H), 7.17-7.25 (m,
5H), 6.34 (t, J = 7.2 Hz, 1H), 3.88 (d, J = 7.2 Hz, 2H); 13C
NMR {1H} (100 MHz, Acetone-d6) δ 143.5, 143.3, 140.8,
137.9, 135.0, 132.9, 130.7, 129.6, 129.4, 129.1, 128.5, 128.3,
128.1, 128.0, 127.8, 126.8, 126.7, 126.6, 126.5, 124.7, 34.0;
HRMS (ESI) calcd. for C25H19 [M-H]﹣ : 319.1491, found:
319.1464.
4,4'-(3-Phenylprop-1-ene-1,1-diyl)bis(methoxybenzene)
(3ae). Colorless oil (139 mg, 84 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.17-7.21 (m, 2H), 7.05-7.11 (m, 7H), 6.80-6.84 (m,
2H), 6.68-6.72 (m, 2H), 6.04 (t, J = 7.6 Hz, 1H), 3.73 (s, 3H),
3.68 (s, 3H), 3.37 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100
MHz, CDCl3) δ 158.9, 158.8, 141.6, 141.4, 135.7, 132.4,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 8
131.2, 128.6, 128.6, 128.5, 126.0, 125.9, 113.7, 113.6, 55.4,
55.3, 36.1; HRMS (ESI) calcd. for C23H22NaO2 [M+Na]﹢ :
353.1512, found: 353.1510.
131.2, 130.0, 128.6, 128.5, 128.5, 128.4, 128.2, 127.6, 127.6,
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127.2, 127.1, 126.2, 126.1, 126.1, 113.8, 113.6, 55.4, 55.3,
36.1, 36.0; HRMS (ESI) calcd. for C22H20NaO [M+Na] ﹢ :
323.1406, found: 323.1398.
3al. A mixture of but-2-ene-1,3-diyldibenzene (Internal
product) and but-3-ene-1,3-diyldibenzene (Terminal product).
4,4'-(3-Phenylprop-1-ene-1,1-diyl)bis(N,N-dimethylaniline)
1
(3af). Yellow oil (119 mg, 67 % yield). H NMR (400 MHz,
CDCl3) δ 7.11-7.29 (m, 9H), 6.71 (d, J = 7.6 Hz, 2H), 6.61 (d,
J = 8.4 Hz, 2H), 6.02-6.06 (m, 1H), 3.50 (d, J = 7.6 Hz, 2H),
2.95 (s, 6H), 2.90 (s, 6H); 13C {1H} NMR (100 MHz, CDCl3)
δ 149.8, 149.5, 142.4, 142.1, 131.9, 130.9, 128.6, 128.5, 128.4,
125.8, 123.7, 112.2, 112.1, 40.7, 40.7, 36.1; HRMS (ESI)
calcd. for C25H29N2 [M+H]﹢: 357.2325, found: 357.2318.
1-Fluoro-4-(1-(4-methoxyphenyl)-3-phenylprop-1-en-1-yl)-
benzene (3ag, E/Z = 2.0:1). Colorless oil (145 mg, 91 % yield).
1H NMR (400 MHz, CDCl3) δ 7.04-7.30 (m, 11H), 6.77-6.95
(m, 2H), 6.12-6.19 (m, 1H), 3.82 (s, 0.68H), 3.76 (s, 2.33H),
3.47 (d, J = 7.6 Hz, 0.47H), 3.42 (d, J = 7.6 Hz, 1.63H); 13C
NMR {1H} (100 MHz, CDCl3) δ 161.0 (d, J = 244.7 Hz),
160.9 (d, J = 244.4 Hz), 159.1, 158.9, 141.1, 139.1 (d, J = 3.0
Hz), 136.0 (d, J = 3.3 Hz), 135.1, 132.0, 131.6 (d, J = 7.9 Hz),
131.1, 129.1 (d, J = 7.8 Hz), 128.6, 128.5, 128.5, 127.5, 126.5,
126.2, 115.2 (d, J = 21.1 Hz), 114.9 (d, J = 21.1 Hz), 113.9,
113.7, 55.4, 55.4, 36.1, 36.0; 19F NMR (376 MHz CDCl3) δ -
115.1, -115.7; HRMS (ESI) calcd. for C22H19FNaO [M+Na]﹢:
341.1312, found: 341.1314.
Colorless oil (62 mg, 60 % yield). 1H NMR (400 MHz, CDCl3)
δ 7.15-7.44 (m, 27.54H), 5.95-5.99 (m, 1.73H), 5.29 (d, J =
1.2 Hz, 1H), 5.05 (d, J = 1.2 Hz, 1H), 3.55 (d, J = 7.6 Hz,
3.64H), 2.79-2.83 (m, 2H), 2.73-2.77 (m, 2H), 2.13 (s, 2.82H),
2.13 (s, 2.45H); 13C NMR {1H} (100 MHz, CDCl3) δ 147.9,
143.7, 142.1, 141.2, 141.1, 135.8, 128.6, 128.6, 128.5, 128.5,
128.4, 128.3, 127.6, 126.9, 126.9, 126.3, 126.1, 126.0, 125.9,
112.8, 37.4, 35.1, 34.9, 16.1; HRMS (ESI) calcd. for C16H15
[M-H]﹣: 207.1178, found: 207.1160.
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3am.
A
mixture of 1-methyl-4-(4-phenylbut-2-en-2-
yl)benzene (Internal product) and 1-methyl-4-(4-phenylbut-1-
en-2-yl)benzene (Terminal product). Colorless oil (60 mg, 54 %
1
yield). H NMR (400 MHz, CDCl3) δ 7.09-7.34 (m, 27H),
5.94-5.96 (m, 1H), 5.92-5.94 (m, 1H), 5.26 (d, J = 1.2 Hz, 1H),
5.00 (d, J = 0.8 Hz, 1H), 3.53 (d, J = 7.6 Hz, 4H), 2.76-2.81
(m, 2H), 2.72-2.76 (m, 2H), 2.34 (s, 3H), 2.31 (s, 6H), 2.11 (s,
3H), 2.11 (s, 3H); 13C NMR {1H} (100 MHz, CDCl3) δ 147.7,
142.2, 141.3, 140.9, 138.3, 137.3, 136.5, 135.6, 129.2, 129.0,
128.6, 128.6, 128.5, 128.4, 126.1, 126.0, 126.0, 126.0, 125.7,
112.0, 37.4, 35.1, 34.9, 21.2, 21.1, 16.1; HRMS (ESI) calcd.
for C17H17 [M-H]﹣: 221.1335, found: 221.1315.
(1-(p-Tolyl)prop-1-ene-1,3-diyl)dibenzene (3ah, E/Z
=
1.5:1). Colorless oil (126 mg, 89 % yield). 1H NMR (400 MHz,
CDCl3) δ 7.12-7.39 (m, 13H), 7.05 (d, J = 8.0 Hz, 1H), 6.23 (t,
J = 7.6 Hz, 1H), 3.47 (d, J = 7.6 Hz, 0.9H), 3.44 (d, J = 7.6 Hz,
1.1H), 2.37 (s, 1.3H), 2.31 (s, 1.7H); 13C NMR {1H} (100
MHz, CDCl3) δ 142.8, 142.5, 142.5, 141.2, 141.2, 140.1,
139.8, 137.0, 136.9, 130.1, 130.0, 129.1, 129.0, 128.6, 128.6,
128.4, 128.2, 127.7, 127.5, 127.4, 127.2, 127.1, 127.0, 126.1,
36.1, 36.0, 21.4, 21.2; HRMS (ESI) calcd. for C22H19 [M-H]﹣:
283.1491, found: 283.1470.
3an.
A
mixture of 1-fluoro-4-(4-phenylbut-2-en-2-
yl)benzene (Internal product) and 1-fluoro-4-(4-phenylbut-1-
en-2-yl)benzene (Terminal product). Colorless oil (61 mg, 54 %
1
yield). H NMR (400 MHz, CDCl3) δ 7.15-7.39 (m, 18H),
6.95-7.04 (m, 5H), 5.90-5.92 (m, 0.79H), 5.88-5.90 (m,
0.78H), 5.23 (d, J = 0.8 Hz, 1H), 5.04 (d, J = 0.8 Hz, 1H), 3.54
(d, J = 7.6 Hz, 3.31H), 2.76-2.80 (m, 2H), 2.71-2.76 (m, 2H),
2.11 (s, 2.35H), 2.11(s, 2.46H); 13C NMR {1H} (100 MHz,
CDCl3) δ 161.1 (d, J = 244.7 Hz), 160.7 (d, J = 244.0 Hz),
146.8, 141.8, 141.0, 139.7 (d, J = 3.1 Hz), 137.2, 134.7, 128.6,
128.5, 128.4, 128.4, 127.7 (d, J = 7.7 Hz), 127.2 (d, J = 7.8
Hz), 126.7, 126.1, 126.0, 115.1 (d, J = 21.2 Hz), 114.8 (d, J =
21.1 Hz), 112.7, 37.4, 35.0, 34.7, 16.1; 19F NMR (376 MHz
CDCl3) δ -115.2, -116.3; HRMS (ESI) calcd. for C16H16F
[M+H]﹢: 227.1231, found: 227.1227.
(1-(4-Fluorophenyl)prop-1-ene-1,3-diyl)dibenzene (3ai, E/Z
1
= 1.4:1). Colorless oil (121 mg, 84 % yield). H NMR (400
MHz, CDCl3) δ 7.17-7.40 (m, 12H), 7.05-7.09 (m, 0.88H),
6.91-6.96 (m, 1.19H), 6.27 (t, J = 8.0 Hz, 0.43H), 6.19 (t, J =
7.6 Hz, 0.59H), 3.44 (d, J = 7.6 Hz, 2H); 13C NMR {1H} (100
MHz, CDCl3) δ 161.0 (d, J = 244.8 Hz), 160.9 (d, J = 244.4
Hz), 142.4, 141.7, 141.6, 141.0, 140.9, 139.8, 138.7 (d, J = 3.3
Hz), 135.8 (d, J = 3.4 Hz), 131.6 (d, J = 7.9 Hz), 130.0, 129.0
(d, J = 7.9 Hz), 128.7, 128.7, 128.5, 128.5, 128.3, 128.2, 127.8,
127.8, 127.4, 127.3, 126.2, 126.2, 115.3 (d, J = 21.1 Hz),
114.9 (d, J = 21.2 Hz), 36.1, 36.0; 19F NMR (376 MHz CDCl3)
δ -115.0, -115.6; HRMS (ESI) calcd. for C21H17FNa [M+Na]+:
311.1206, found: 311.1202.
3ao.
A
mixture of 1-chloro-4-(4-phenylbut-2-en-2-
yl)benzene (Internal product) and 1-chloro-4-(4-phenylbut-1-
en-2-yl)benzene (Terminal product). Colorless oil (61 mg, 50 %
1
yield). H NMR (400 MHz, CDCl3) δ 7.14-7.35 (m, 16H),
5.94-5.97 (m, 0.40H), 5.92-5.94 (m, 0.40H), 5.26 (d, J = 0.8
Hz, 1H), 5.06 (d, J = 0.8 Hz, 1H), 3.53 (d, J = 7.6 Hz, 1.66H),
2.75-2.79 (m, 2H), 2.71-2.75 (m, 2H), 2.10 (s, 1.32H), 2.10 (s,
1.15H); 13C NMR {1H} (100 MHz, CDCl3) δ 146.8, 142.1,
141.8, 140.9, 139.6, 134.7, 133.3, 132.6, 128.7, 128.6, 128.5,
128.5, 128.5, 128.4, 127.6, 127.4, 127.1, 126.2, 126.1, 113.4,
37.3, 35.1, 34.7, 16.0; HRMS (ESI) calcd. for C16H16Cl [M+H]
﹢: 243.0936, found: 243.0930.
(1-(4-Chlorophenyl)prop-1-ene-1,3-diyl)dibenzene (3aj, E/Z
1
= 1.3:1). Colorless oil (125 mg, 82 % yield). H NMR (400
MHz, CDCl3) δ 7.15-7.41 (m, 14H), 6.28 (t, J = 7.6 Hz,
0.45H), 6.24 (t, J = 8.0 Hz, 0.53H), 3.45 (d, J = 7.6 Hz, 2H);
13C NMR {1H} (100 MHz, CDCl3) δ 142.1, 141.5, 141.1,
140.8, 140.7, 139.5, 138.4, 133.2, 133.0, 131.5, 130.0, 128.7,
128.7, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.4, 128.4,
127.5, 127.5, 127.4, 126.3, 126.2, 36.1, 36.0; HRMS (ESI)
calcd. for C21H17ClNa [M+Na]﹢: 327.0911, found: 327.0904.
(1-(4-Methoxyphenyl)prop-1-ene-1,3-diyl)dibenzene (3ak,
3ap.
A
mixture of 1-methoxy-4-(4-phenylbut-2-en-2-
yl)benzene (Internal product) and 1-methoxy-4-(4-phenylbut-
1-en-2-yl)benzene (Terminal product). Colorless oil (67 mg,
1
1
E/Z = 2.3:1). Colorless oil (138 mg, 92 % yield). H NMR
56 % yield). H NMR (400 MHz, CDCl3): internal isomer: δ
(400 MHz, CDCl3) δ 7.15-7.39 (m, 12H), 6.77-6.93 (m, 2H),
6.22 (t, J = 7.6 Hz, 0.28H), 6.17 (t, J = 7.6 Hz, 0.70H), 3.81 (s,
0.83H), 3.76 (s, 2.22H), 3.48 (d, J = 7.6 Hz, 0.55H), 3.43 (d, J
= 7.6 Hz, 1.46H); 13C NMR {1H} (100 MHz, CDCl3) δ 159.0,
158.8, 143.0, 142.2, 142.0, 141.3, 141.2, 140.2, 135.3, 132.2,
7.19-7.35 (m, 7H), 6.83-6.85 (m, 2H), 5.90-5.91 (m, 0.51H),
5.87-5.89 (m, 0.49H), 3.78 (s, 3H), 3.54 (d, J = 7.2 Hz, 2H),
2.11 (s, 1.62H), 2.11 (s, 1.43H); 13C NMR {1H} (100 MHz,
CDCl3) δ 158.7, 141.4, 136.3, 135.1, 128.6, 128.6, 126.9,
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The Journal of Organic Chemistry
Reaction optimization, mechanistic studies and copies for 1H
126.0, 125.3, 113.7, 55.4, 35.1, 16.1; HRMS (ESI) calcd. for
C17H19O [M+H]﹢: 239.1430, found: 239.1426.
NMR, 13C NMR and 19F NMR of the products (PDF).
1
2
3
4
5
6
7
8
9
3aq.
A
mixture of 1-isobutyl-4-(4-phenylbut-2-en-2-
AUTHOR INFORMATION
Corresponding Author
yl)benzene (Internal product) and 1-isobutyl-4-(4-phenylbut-1-
en-2-yl)benzene (Terminal product). Colorless oil (75 mg, 57 %
yield). H NMR (400 MHz, CDCl3) δ 7.16-7.36 (m, 21H),
1
*E-mail: hanmin@ustc.edu.cn
*E-mail: hcom@licp.cas.cn
Notes
7.06-7.12 (m, 6H), 5.96-5.98 (m, 1H), 5.94-5.96 (m, 1H), 5.28
(d, J = 1.2 Hz, 1H), 5.01 (d, J = 0.8 Hz, 1H), 3.54 (d, J = 7.6
Hz, 4H), 2.75-2.81 (m, 4H), 2.46 (d, J = 7.2 Hz, 2H), 2.43 (d,
J = 7.2 Hz, 4H), 2.12 (s, 3H), 2.12 (s, 3H), 1.79-1.90 (m, 3H),
0.90 (d, J = 6.8 Hz, 12H), 0.88 (s, 6H); 13C NMR {1H} (100
MHz, CDCl3) δ 147.7, 142.2, 141.3, 141.1, 141.0, 140.4,
138.4, 135.6, 129.2, 129.1, 128.6, 128.5, 128.4, 126.0, 126.0,
125.9, 125.9, 125.5, 111.9, 45.2, 45.2, 37.4, 35.1, 35.0, 30.4,
22.5, 16.0; HRMS (ESI) calcd. for C20H23 [M-H]﹣: 263.1804,
found: 263.1783.
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
This research was supported by the National Natural Science
Foundation of China (21672199 and 21790333), the CAS Inter-
disciplinary Innovation Team, the Anhui provincial Natural Sci-
ence Foundation (1708085MB28), and the Fundamental Research
Funds for the Central Universities.
3ar.
(trifluoromethyl)benzene (Internal product) and 1-(4-
phenylbut-1-en-2-yl)-4-(trifluoromethyl)benzene (Terminal
A
mixture
of
1-(4-phenylbut-2-en-2-yl)-4-
1
product). Colorless oil (70 mg, 51 % yield). H NMR (400
MHz, CDCl3) δ 7.46-7.59 (m, 12H), 7.14-7.32 (m, 15H), 6.03-
6.05 (m, 1H), 6.01-6.03 (m, 1H), 5.34 (s, 1H), 5.15 (d, J = 1.2
Hz, 1H), 3.56 (d, J = 7.2 Hz, 4H), 2.79-2.83 (m, 2H), 2.72-
2.76 (m, 2H), 2.14 (s, 3H), 2.14 (s, 3H); 13C NMR {1H} (100
MHz, CDCl3) δ 147.2, 146.9, 144.9, 141.6, 140.6, 134.8,
129.1, 129.0, 128.7 (q, J = 3.5 Hz), 126.6, 126.3, 126.2, 126.1,
125.8, 125.8, 125.5 (q, J = 3.7 Hz), 125.3 (q, J = 3.7 Hz),
123.1, 123.1, 114.8, 37.2, 35.2, 34.7, 16.0; 19F NMR (376
MHz CDCl3) δ -62.3, -62.4; HRMS (ESI) calcd. for
C17H15F3Na [M+Na]﹢: 299.1018, found: 299.1014.
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>
1
20:1). Colorless oil (63 mg, 50 % yield). H NMR (400 MHz,
CDCl3) δ 7.29-7.33 (m, 2H), 7.22-7.26 (m, 3H), 7.12-7.17 (m,
1H), 7.06-7.09 (m, 4H), 5.70 (t, J = 7.2 Hz, 1H), 2.97 (d, J =
7.2 Hz, 2H), 1.08 (s, 9H); 13C NMR {1H} (100 MHz, CDCl3) δ
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1-Fluoro-4-(3-phenylprop-1-en-1-yl)benzene (3at, E/Z >
20:1). Colorless oil (27 mg, 25 % yield). H NMR (400 MHz,
1
CDCl3) δ 7.20-7.33 (m, 7H), 6.94-6.99 (m, 2H), 6.38 (d, J =
15.6 Hz, 1H), 6.22-6.30 (m, 1H), 3.52 (d, J = 6.4 Hz, 2H); 13
C
NMR {1H} (100 MHz, CDCl3) δ 160.9 (d, J = 244.5 Hz),
140.1, 133.6 (d, J = 3.1 Hz), 129.9, 129.1 (double peak), 128.7,
128.6, 127.6 (d, J = 7.7 Hz), 126.3, 115.3 (d, J = 21.3 Hz),
39.3; 19F NMR (376 MHz CDCl3) δ -115.3; HRMS (ESI)
calcd for C15H12F [M-H]﹣: 211.0928; found, 211.0920.
1-Isobutyl-4-(3-phenylprop-1-en-1-yl)benzene (3au, E/Z >
20:1). Colorless oil (33 mg, 26 % yield). H NMR (400 MHz,
1
CDCl3) δ 7.18-7.31 (m, 7H), 7.05-7.07 (m, 2H), 6.41 (d, J =
15.6 Hz, 1H), 6.26-6.34 (m, 1H), 3.51 (d, J = 6.8 Hz, 2H),
2.42 (d, J = 7.2 Hz, 2H), 1.78-1.88 (m, 1H), 0.87 (d, J = 6.4
Hz, 6H) ; 13C NMR {1H} (100 MHz, CDCl3) δ 140.9, 140.5,
135.1, 131.1, 129.4, 128.8, 128.6, 128.3, 126.3, 126.0, 45.3,
39.5, 30.4, 22.5; HRMS (EI) calcd for C19H22[M]+: 250.1717,
found: 250.1728.
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ASSOCIATED CONTENT
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