Stereoselective Rhodium-Catalyzed Isomerization of Stereoisomeric Mixtures of Arylalkenes

Article abstract of DOI:10.1055/s-0040-1707166

A new efficient method for the synthesis of a high ratio of E -alkenes from E / Z mixtures of alkenes with B ₂pin ₂in the presence of a rhodium catalyst is described. This reaction features mild reaction conditions, broad functional group tolerance, and highly great application potential.

Full text of DOI:10.1055/s-0040-1707166

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2020, 52, A–H
paper
A
en
H. Yang et al.
Paper
Synthesis
Stereoselective Rhodium-Catalyzed Isomerization of Stereoisomeric
Mixtures of Arylalkenes
Hongxuan Yang
B2pin2 (5 mol%)
[Rh(cod)Cl]2 (3 mol%)
R
R
Wenke Dong
Wencan Wang
Tao Li*
Ar
Ar
Xantphos (9 mol%)
DME, 60 °C, 8 h
E/Z mixture
E-Arylalkenes
• E/Z >10:1
R = alkyl, aryl
Wanxiang Zhao*
• 30 examples
• neutral condition
• good FG compatibility
State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan University,
Changsha, Hunan 410082, P. R. China
• 86–91% yield
zhaowanxiang@hnu.edu.cn
Received: 29.05.2020
Accepted after revision: 02.06.2020
Published online: 06.07.2020
For example, Jung’s group disclosed a palladium-catalyzed
Z- to E-alkene isomerization using excessive Bu3SnH as hy-
drogen donors.6r Moreover, the isomerization of alkenes
may involve the uncontrollable migration of the double
bonds, or reversible interconversion between Z- and E-
alkenes, which result in poor regio- and stereoselectivi-
ty.4,6f,6r–t Therefore, it is highly desirable to develop reliable,
mild, and neutral protocols to generate alkenes with excel-
lent stereoselectivity. Herein, we report a rhodium-cata-
lyzed isomerization of Z- and E-alkene mixtures to pure E-
alkenes in the absence of external H source under neutral
reaction conditions.
DOI: 10.1055/s-0040-1707166; Art ID: ss-2020-g0085-op
Abstract A new efficient method for the synthesis of a high ratio of E-
alkenes from E/Z mixtures of alkenes with B2pin2 in the presence of a
rhodium catalyst is described. This reaction features mild reaction con-
ditions, broad functional group tolerance, and highly great application
potential.
Key words isomerization, stereoselectivity, rhodium, alkene, inter-
conversion
Alkenes are ubiquitous building blocks in organic syn-
thesis and materials science as they can be efficiently con-
verted into a variety of functional groups and serve as the
precursors for polymerization.1 As a result, the alkene syn-
thesis is a topic of wide interest in synthetic chemistry.
However, conventional methods for alkene formation usu-
ally suffer from poor stereoselectivity (e.g., Wittig reaction
and olefin metathesis),2 although the C=C bonds with dif-
ferent stereochemistry probably display different physical
and chemical properties. From the perspective of atom
economy, isomerization of Z- and E-alkene mixtures to a
specific configuration in high selectivity is an appealing
methodology for preparing alkenes. Over the past two de-
cades, tremendous efforts have been dedicated to alkene
isomerization reactions to get the geometrically pure iso-
mers. Several synthetic methodologies, including radical,3
photochemical reactions,4 and acid/base-catalyzed isomer-
ization,5 have been established to obtain E-alkenes (Scheme
1a) or contra-thermodynamic products of Z-alkene, but
some of them require relatively harsh reaction conditions.
Recently, transition metal catalysts, including Cr,6a Fe,6b,c
Ni,6d Co,6e,f Mo,6g Ru,6h–o Rh,6p,q Pd,6r–u and Ir,6v–z have been
employed in catalyzing this type of transformation. Howev-
er, these approaches commonly need external H sources.
(a) Traditional E/Z isomerization reactions of alkenes
radical reagents
R
R'
R
R
R'
acids/bases
n
n
1,2-disubstituted
alkenes
E/Z mixture
photochemical
reagents
R'
n
E-selective
isomerization
transition-metal
catalysts
(b) Rhodium-Catalyzed alkene isomerization (this work)
R
R
Rh
Ar
Ar
1,2-disubstituted
alkenes
E-selective
isomerization
B2pin2 (5 mol%)
E/Z mixture
Scheme 1 Isomerization of alkenes
We began our investigation by evaluating the amount of
B2pin2 using arylalkenes 1a (E/Z = 1.7:1) as the model
substrate and DME as the solvent. In the presence of 1.1
equivalents of B2pin2, vinylboronate 2a was formed via Rh-
catalyzed dehydrogenative borylation in 75% yield (Table 1,
entry 1). Pleasingly, we found that the yield of the desired
E-1a increased with the decrease of the amount of B2pin2
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Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
H. Yang et al.
Paper
Synthesis
(entries 1–4), and 92% E-1a, 5% Z-1a, and a small amount of
vinylboronate 2a were obtained when 5 mol% of B2pin2 was
used. With the decrease of ligand or B2pin2, the yield
dropped dramatically, suggesting that both of them played
a crucial role in this reaction. We also examined other
monodentate and bidentate phosphine ligands using
[Rh(cod)Cl]2 as the catalyst precursor, such as PCy3, PPh3,
DPPP, and DPPB, but all of them gave lower yields than
Xantphos (entries 7–10). We next turned our attention to
screen the solvent. As shown in Table 1, we found that the
solvent (EtOAc and MeCN) had no significant effect on the
reaction (entries 11, 12). In addition, lower yield was ob-
served when reaction time was reduced to 0.1 hour due to
incomplete conversion (entry 13).
naphthalene, furan, thiophene, and pyridine were tolerated
as well (1l–p). It is worth noting that this isomerization
showed good functional-group tolerance to the alkyl sub-
stituent (R2), such as alkene, Cl, ether, and acetal (1r–t).
However, the conversions were unsuccessful when 1,2-di-
alkylalkenes and trisubstituted alkenes were used as sub-
strates due to the double bond migration and steric effect.
Diphenylethene derivatives were all suitable for this trans-
formation to produce the E-products in excellent yields
(1w–1ac).
To explore the application of this method, the resvera-
trol derivative E-3 was synthesized. Resveratrol7 has a spe-
cial biological activity and studies have found that the
physiological activity of E-resveratrol is stronger than the
Z-structure. Starting from commercially available 4-ethoxy-
benzyltriphenylphosphonium bromide and 3,5-dimethoxy-
benzaldehyde, the E/Z mixture of 3 was prepared in 81%
yield via Wittig reaction, which then underwent Rh-cata-
lyzed isomerization to provide the E-3 in 86% yield (Scheme
3).
Table 1 Optimization of Reaction Conditionsa
H
nPr
H
B2pin2 (X equiv)
[Rh(cod)Cl]2 (3 mol%)
H
nPr
H
E-1a
Ph
H
Bpin
Xantphos (9 mol%)
DME, 60 °C, 8 h
Ph
2a
1a E:Z = 1.7:1
To get more insightful information of isomerization
mechanism, we treated the Z-1a under the standard reac-
tion conditions, and discovered that the isomerized product
E-1a was generated in 93% yield (Scheme 4). Besides, an-
other control experiment was also conducted by using
pure E-1ab as starting material, which detected 92% E-1ab
Ph
nPr
Entry
Ligand
B2pin2 (X equiv) E-1a (%)b
ratio (E/Z)c 2a (%)b
1d
0
0
75
61
15
<5
0
Xantphos
1.1
0.7
0.2
0.05
0.05
-
Xantphos
Xantphos
Xantphos
-
2
6
>15:1
15:1
15:1
1.7:1
1.7:1
3
68
92
61
62
1
4
and 5% Z-1ab by H NMR testing. The results indicate that
5
our reaction conditions equilibrate the E/Z-isomer mixture,
and at room temperature a high (>10:1) ratio of E-isomer is
formed. Therefore, a possible catalytic cycle is proposed in
Scheme 5. Initially, the [Rh(cod)Cl]2 reacted with B2pin2 to
form Rh–Bpin,8 which then underwent 1,2-migration inser-
tion and -H-elimination to generate the Rh–H species. The
Rh–H generated via dehydrogenative borylation is thought
to be the active catalyst for the alkene isomerization, which
inserted into the Z-1 to afford the intermediated I. Subse-
quently, the rotation and -H-elimination produced the E-1
and regenerated the Rh–H catalyst. Since these reactions
were proceeded by a -H-elimination mechanism, other
hydride sources, such as MeOH and i-PrOH, were used to
check the validity. The experimental results showed that
only a small amount of E-alkene was generated.
In conclusion, we have developed an efficient method
for the stereoselective preparation of E-arylalkenes from
the E/Z mixtures via Rh-catalyzed isomerization. The mech-
anistic studies indicated that the Rh–H generated via dehy-
drogenative borylation9 is the active catalyst in this alkene
isomerization. It is noteworthy that the isomerization reac-
tion showed mild reaction conditions and excellent func-
tional group suitability. These transformations have great
potential for the synthesis of functionalized molecules. Fur-
ther research on dehydroboration of this reaction is cur-
rently underway in our laboratory.
Xantphos
6
0
PCy3
PPh3
0.05
0.05
0.05
0.05
0.05
0.05
0.05
7
8
70
69
66
70
91
92
78
2.5:1
2.4:1
2.1:1
2.5:1
15:1
0
0
DPPP
9
0
DPPB
10
11e
12f
13g
0
Xantphos
Xantphos
Xantphos
<5
<5
<5
15:1
3.3:1
a Unless otherwise noted, all reactions were carried out with 1a (0.30
mmol), B2pin2 (0.015 mmol), [Rh(cod)Cl]2 (3 mol%) and ligand (18 mol%
for monodentate phosphines and 9 mol% for bidentate phosphines).
b Yields were determined by 1H NMR analysis with CH2Br2 (51.9 mg) as
internal standard.
c The ratio of E/Z was determined by 1H NMR analysis.
d The reaction proceeded at 80 °C for 19 h.
e EtOAc was used as the solvent .
f MeCN was used as the solvent.
g Reaction time: 0.1 h.
With the optimal reaction conditions determined, we
then looked into the scope of arylalkenes. As demonstrated
in Scheme 2, a variety of arylalkenes with different func-
tional groups proved to be good substrates for this isomeri-
zation. The substrates with a range of electronically diverse
substituents at the para-position, including NO2, NMe2,
OMe, SMe, F, Br, and Cl (1b–j) were also applicable to this
transformation. In addition, other aromatic rings, such as
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

C
H. Yang et al.
Paper
Synthesis
H
R2
H
H
R2
H
[Rh(cod)Cl]2 (3 mol%)
Xantphos (9 mol%), B2pin2 (5 mol%)
Ar
Ar
DME (1.0 mL)
60 °C, 8 h
R1
R1
1, E/Z mixture
E-1
H
nPr
H
H
nPr
H
H
nPr
H
H
nPr
H
H
nPr
H
H
nPr
H
O2N
E-1b, 89% (>15:1)
Me2N
E-1c, 90% (>15:1)
MeO
E-1d, 91% (12:1)
MeS
Ph
E-1f, 91% (11:1)
E-1a, 89% (15:1)
nPr
E-1e, 87% (11:1)
nPr
H
H
nPr
H
H
nPr
H
H
nPr
H
H
H
H
nPr
H
MeO
H
TBSO
E-1g,87%(15:1)
F
Br
Cl
E-1h, 88% (8:1)
E-1i, 88% (8:1)
E-1j, 88% (10:1)
E-1k, 90% (12:1)
E-1l, 90% (12:1)
H
nPr
Me
Me
Me
nPr
H
nPr
H
H
nPr
H
H
H
H
H
Cl
H
4
H
O
O
S
H
N
O
E-1m, 90% (10:1)
E-1n, 89% (8:1)
E-1o, 90% (10:1)
E-1p, 91% (>15:1)
iBu
E-1q, 90% (10:1)
Bn
E-1r, 90% (9:1)
H
H
H
Ph
H
H
H
OMe
O
H
H
4
4
H
H
O
E-1s, 91% (12:1)
E-1t, 90% (12:1)
E-1u, 90% (13:1)
E-1v, 91% (11:1)
E-1w, 91% (>15:1)
H
Ph
H
H
Ph
H
H
Ph
H
H
Ph
H
H
Ph
H
H
Ph
H
F
H3C
O
F
MeO
E-1y, 91% (>15:1)
F3C
F
O
O
E-1x, 90% (>15:1)
E-1z, 91% (>15:1)
E-1aa, 91% (>15:1)
E-1ab, 90% (>15:1)
E-1ac, 88% (>15:1)
Scheme 2 Scope of Alkenes. Reagents and conditions: Unless otherwise noted, all reactions were carried out with 1 (0.30 mmol), B2pin2 (0.015 mmol),
[Rh(cod)Cl]2 (3 mol%), and Xantphos (9 mol%) in 1.0 mL DME at 60 °C. Isolated yields are shown. The ratio of E/Z was determined by 1H NMR analysis.
EtO
[Rh(cod)Cl]2 (3 mol%)
Xantphos (9 mol%)
EtO
EtO
a. nBuLi (1.2 equiv)
Ph
H
nPr
H
Ph
H
H
OMe
THF, –78 °C to rt
B2pin2(5 mol%)
DME, 60 °C, 8 h
nPr
+PPh3
Br–
b. 3,5-dimethoxybenzaldehyde
E-1a, 93% (15:1)
Z-1a
3, 81% (2:1)
OMe
[Rh(cod)Cl]2 (3 mol%)
Xantphos (9 mol%)
Ph
H
H
Ph
H
H
B2pin2(5 mol%)
DME, 60 °C, 8 h
OMe
OMe
[Rh(cod)Cl]2 (3 mol%)
OMe
E-1ad, 92% (>15:1)
Xantphos (9 mol%)
E-1ad
B2pin2 (5 mol%)
Scheme 4 Control experiment
DME (1.0 mL), 60 °C, 8 h
E-3 86%
OMe
Scheme 3 Synthesis of resveratrol derivative
Unless otherwise noted, all reactions were conducted in oven-dried
vials with a magnetic stir bar under N2 atmosphere. Solvents were pu-
rified under N2 using a solvent purification system. [RhCl(cod)]2 was
prepared according to literature procedure and all characterization
data are in accordance with the literature.10 Phosphine ligands, bases
and bis(pinacolate)diboron (B2pin2) were all purchased from Energy
Chemicals Inc. and used as received. Analytical TLC was performed
using silica gel plates. Visualization was by ultraviolet fluorescence,
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

D
H. Yang et al.
Paper
Synthesis
(E)-1-Nitro-4-(pent-1-en-1-yl)benzene (E-1b)
Yellow oil; yield: 50.9 mg (89%); E/Z >15:1.
1H NMR (400 MHz, CDCl3):  = 8.15 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 8.5
Hz, 2H), 6.50–6.40 (m, 2H), 2.31–2.19 (m, 2H), 1.59–1.48 (m, 2H),
0.97 (t, J = 7.4 Hz, 3H).
13C NMR (100 MHz, CDCl3):  = 146.5, 144.6, 136.5, 128.4, 126.5,
124.1, 35.4, 22.3, 13.9.
Rh
Ar
Ar
R
R
B2pin2, ligand
E/Z-Arylalkenes
E-Arylalkenes
[RhCl(cod)]2
B2pin2, ligand
Rh-Bpin
R
Ar
R
Ar
E/Z-1
migration insertion
Bpin
β-H-elimination
2
These spectroscopic data match those previously reported.12
Rh-H
(E)-N,N-Dimethyl-4-(pent-1-en-1-yl)aniline (E-1c)
Colorless oil; yield: 50.9 mg (90%); E/Z >15:1.
Ar
R
Ar
R
Z-1
IR (neat): 2956, 2925, 2870, 2860, 1612, 1522, 1352, 1165, 962 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.23 (d, J = 8.0 Hz, 2 H), 6.67 (d, J = 8.0
Hz, 2 H), 6.29 (d, J = 15.8 Hz, 1 H), 6.06–5.96 (m, 1 H), 2.92 (s, 6 H),
2.20–2.10 (m, 2 H) , 1.54–1.40 (m, 2 H), 0.94 (t, J = 7.4 Hz, 3 H).
Rh
Rh
H
H
R
Ar
Ar
H
I
II
R
H
13C NMR (100 MHz, CDCl3):  = 149.8, 129.7, 127.02, 126.87, 126.9,
112.9, 40.8, 35.3, 23.0, 13.9.
HRMS (APCI): m/z calcd for C13H20N+ [M + H]+: 190.1590; found:
190.1590.
Scheme 5 Proposed catalytic cycles
(E)-1-Methoxy-4-(pent-1-en-1-yl)benzene (E-1d)
Colorless oil; yield: 50.9 mg (91%); E/Z = 12:1.
and/or phosphomolybdic acid, and/or KMnO4. Flash column chroma-
tography was performed using EM Science (200–300 mesh) silica gel.
1H and 13C NMR spectra were recorded on Bruker 400 MHz at 20 °C
with CDCl3 as solvent and TMS as an internal standard. The data are
reported as follows: chemical shift (ppm), multiplicity (standard ab-
breviations), coupling constant J (Hz), and integration. High-resolu-
tion mass spectra were recorded on a Bruker Maxis System. IR spectra
were collected on a Spectrum BX FTIR from PerkinElmer and reported
1H NMR (400 MHz, CDCl3):  = 7.26 (d, J = 7.9 Hz, 2 H), 6.82 (d, J = 7.8
Hz, 2 H), 6.31 (d, J = 15.7 Hz, 1 H), 6.12–6.00 (m, 1 H), 3.77 (s, 3 H),
2.22–2.06 (m, 2 H), 1.54–1.40 (m, 2 H), 0.94 (t, J = 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 158.7, 130.9, 129.3, 128.9, 127.1,
114.0, 55.3, 35.2, 22.8, 13.9.
These spectroscopic data match those previously reported.13
in unit of cm–1
.
The preparation of the starting stereoisomeric mixtures of alkenes 1
as well as optimization of the reaction conditions are described in the
Supporting Information.
(E)-Methyl[4-(pent-1-en-1-yl)phenyl]sulfane (E-1e)
Colorless oil; yield: 50.0 mg (87%); E/Z = 11:1.
IR (neat): 2924, 2870, 1493, 1464, 1458, 1437, 1093, 966, 839, 793
cm–1
.
Stereoselective Rhodium-Catalyzed Isomerization of Stereoiso-
meric Mixtures of Arylalkenes; General Procedure
1H NMR (400 MHz, CDCl3):  = 7.25 (d, J = 7.9 Hz, 2 H), 7.17 (d, J = 7.9
Hz, 2 H), 6.32 (d, J = 15.8 Hz, 1 H), 6.22–6.13 (m, 1 H), 2.45 (s, 3 H),
2.21–2.13 (m, 2 H), 1.53–1.39 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 136.6, 135.2, 130.6, 129.3, 127.0,
126.4, 35.2, 22.7, 16.2, 13.9.
In
a N2-filled glovebox, an oven-dried vial was charged with
[Rh(cod)Cl]2 (4.5 mg, 0.009 mmol), Xantphos (15.6 mg, 0.027 mmol),
and DME (1.0 mL). After stirring for 20 min at r.t., to the resulting
solution was added B2pin2 (3.8 mg, 0.05 equiv), and the mixture was
stirred for an additional 10 min at r.t. Next, the alkene was added by a
syringe, followed by the addition of DME (0.5 mL). The vial was sealed
with a Teflon-lined cap, removed from the glovebox, and the contents
were stirred at 60 °C. The reaction mixture was filtered through Celite
and washed with DCM. The solvent was removed under vacuo. The
residue was purified by silica gel chromatography using petroleum
ether as the eluent to afford the desired products.
HRMS (APCI): m/z calcd for C12H17S+ [M + H]+: 193.1045; found:
193.1045.
(E)-4-(Pent-1-en-1-yl)-1,1′-biphenyl (E-1f)
Colorless oil; yield: 60.6 mg (91%); E/Z = 11:1.
IR (neat): 2976, 2958, 2929, 1487, 1408, 1379, 1371, 1348, 1311,
1165, 1147, 1128, 866, 764, 696 cm–1
.
(E)-Pent-1-en-1-ylbenzene (E-1a)
1H NMR (400 MHz, CDCl3):  = 7.59 (d, J = 7.5 Hz, 2 H), 7.53 (d, J = 7.8
Hz, 2 H), 7.36–7.30 (m, 4 H), 7.33 (t, J = 7.2 Hz, 1 H), 6.42 (d, J = 15.8
Hz, 1 H), 6.33–6.22 (m, 1 H), 2.26–2.16 (m, 2 H), 1.56–1.45 (m, 2 H),
0.97 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 141.0, 139.7, 137.2, 131.4, 129.6,
128.9, 127.31, 127.26, 127.0, 126.5, 35.3, 22.7, 13.9.
Colorless oil; yield: 38.9 mg (89%); E/Z = 15:1.
1H NMR (400 MHz, CDCl3):  = 7.36–7.24 (m, 4 H), 7.21–7.14 (m, 1 H),
6.38 (d, J = 15.9 Hz, 1 H), 6.27–6.17 (m, 1 H), 2.22–2.14 (m, 2 H), 1.56–
1.41 (m, 2 H), 0.95 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 138.1, 131.1, 130.1, 128.6, 126.9,
+
HRMS (APCI): m/z calcd for C17H19 [M + H]+: 223.1481; found:
223.1481.
126.1, 35.3, 22.7, 13.9.
These spectroscopic data match those previously reported.11
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

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Synthesis
(E)-tert-Butyldimethyl[4-(pent-1-en-1-yl)phenoxy]silane (E-1g)
Colorless oil; yield: 72.0 mg (87%); E/Z = 15:1.
1H NMR (400 MHz, CDCl3):  = 7.80–7.73 (m, 3 H), 7.67 (s, 1 H), 7.58
(d, J = 8.6 Hz, 1 H), 7.46–7.37 (m, 2 H), 6.54 (d, J = 15.8 Hz, 1 H), 6.42–
6.29 (m, 1 H), 2.28–2.20 (m, 2 H), 1.71–1.39 (m, 2 H), 0.98 (t, J = 7.3
Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 135.6, 133.9, 132.8, 131.6, 130.2,
128.2, 127.95, 127.76, 126.2, 125.6, 125.4, 123.8, 35.4, 22.7, 13.9.
IR (neat): 2958, 2929, 2860, 1604, 1512, 1504, 1263, 1255, 964, 916,
839, 798, 781 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.21 (d, J = 6.0 Hz, 2 H), 6.76 (d, J = 7.8
Hz, 2 H), 6.31 (d, J = 15.8 Hz, 1 H), 6.15–5.99 (m, 1 H), 1.53–1.42 (m, 2
H), 1.53–1.40 (m, 2 H), 1.02–0.90 (m, 12 H), 0.18 (s, 6 H).
These spectroscopic data match those previously reported.18
13C NMR (100 MHz, CDCl3):  = 154.8, 131.4, 129.4, 129.0, 127.0,
120.3, 35.3, 25.9, 22.8, 18.4, 13.9, -4.3.
HRMS (APCI): m/z calcd for C17H29OSi+ [M + H]+: 277.1982; found:
277.1982.
(E)-5-(Pent-1-en-1-yl)benzo[d][1,3]dioxole (E-1m)
White solid; yield: 51.8 mg (91%); E/Z = 10:1.
1H NMR (400 MHz, CDCl3):  = 6.89 (s, 1 H), 6.79–6.68 (m, 2 H), 6.28
(d, J = 15.7 Hz, 1 H), 6.09–5.99 (m, 1 H), 5.91 (s, 2 H), 2.18– 2.10 (m, 2
H), 1.52–1.41 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 148.1, 146.7, 132.6, 129.6, 129.4,
120.3, 108.3, 105.5, 101.0, 35.1, 22.8, 13.9.
(E)-1-Fluoro-4-(pent-1-en-1-yl)benzene (E-1h)
Colorless oil; yield: 43.2 mg (88%); E/Z = 8:1.
1H NMR (400 MHz, CDCl3):  = 7.34–7.26 (m, 2 H), 7.02–6.91 (m, 2 H),
6.34 (d, J = 15.8 Hz, 1 H), 6.22–6.07 (m, 1 H), 2.22–2.11 (m, 2 H), 1.55–
1.43 (m, 2 H), 0.95 (t, J = 7.3 Hz, 3 H).
These spectroscopic data match those previously reported.19
(E)-2-(Pent-1-en-1-yl)furan (E-1n)
13C NMR (100 MHz, CDCl3):  = 162.0 (d, J = 243.0 Hz), 134.2 (d, J = 3.4
Hz), 130.9 (d, J = 2.2 Hz), 128.9, 127.4 (d, J = 7.8 Hz), 115.4 (d, J = 21.5
Hz), 35.2, 22.7, 13.9.
Yellow oil; yield: 36.7 mg (89%); E/Z = 8:1.
1H NMR (400 MHz, CDCl3):  = 7.35–7.26 (m, 1 H), 6.37–6.30 (m, 1 H),
6.26–6.08 (m, 3 H), 2.19–2.10 (m, 2 H), 1.53–1.42 (m, 2 H), 0.94 (t, J =
7.4 Hz, 3 H).
These spectroscopic data match those previously reported.14
(E)-1-Bromo-4-(pent-1-en-1-yl)benzene (E-1i)
Colorless oil; yield: 59.1 mg (88%); E/Z = 6:1.
1H NMR (400 MHz, CDCl3):  = 7.39 (d, J = 7.5 Hz, 2 H), 7.19 (d, J = 7.6
Hz, 2 H), 6.31 (d, J = 15.9 Hz, 1 H), 6.26–6.15 (m, 1 H), 2.21–2.13 (m, 2
H), 1.54–1.42 (m, 2 H), 0.95 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 153.5, 141.3, 130.2, 118.8, 111.2,
106.0, 35.0, 22.6, 13.9.
HRMS (APCI): m/z calcd for C9H13O+ [M + H]+: 137.0961; found:
137.0961.
These spectroscopic data match those previously reported.19
13C NMR (100 MHz, CDCl3):  = 137.0, 132.0, 131.6, 128.9, 127.6,
120.5, 35.2, 22.6, 13.9.
These spectroscopic data match those previously reported.15
(E)-2-(But-1-en-1-yl)thiophene (E-1o)
Yellow oil; yield: 40.9 mg (90%); E/Z = 10:1.
IR (neat): 2960, 2925, 2852, 1660, 1633, 696 cm–1
.
(E)-1-Chloro-4-(pent-1-en-1-yl)benzene (E-1j)
Colorless oil; yield: 47.5 mg (88%); E/Z = 10:1.
1H NMR (400 MHz, CDCl3):  = 7.28–7.21 (m, 4 H), 6.32 (d, J = 15.9 Hz,
1 H), 6.24–6.13 (m, 1 H), 2.23–2.10 (m, 2 H), 2.54–2.41 (m, 2 H), 0.94
(t, J = 7.3 Hz, 3 H).
1H NMR (400 MHz, CDCl3):  = 7.09–7.03 (m, 1 H), 6.95–6.89 (m, 1 H),
6.88–6.81 (m, 1 H), 6.50 (d, J = 15.7 Hz, 1 H), 6.11–6.01 (m, 1 H), 2.18–
2.11 (m, 2 H), 1.53–1.42 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 143.3, 131.1, 127.3, 124.3, 123.3,
123.1, 35.1, 22.6, 13.9.
13C NMR (100 MHz, CDCl3):  = 136.6, 132.4, 131.8, 128.9, 128.7,
HRMS (APCI): m/z calcd for C9H13S+ [M + H]+: 153.0732; found:
127.2, 35.2, 22.6, 13.9.
153.0732.
These spectroscopic data match those previously reported.16
(E)-4-(But-1-en-1-yl)pyridine (E-1p)
(E)-1-Methoxy-2-(pent-1-en-1-yl)benzene (E-1k)
Colorless oil; yield: 47.5 mg (90%); E/Z = 12:1.
Yellow oil; yield: 40.0 mg (91%); E/Z >15:1.
IR (neat): 2958, 2927, 1599, 968 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.41 (d, J = 7.5 Hz, 1 H), 7.17 (t, J = 7.7
Hz, 1 H), 6.89 (t, J = 7.4 Hz, 1 H), 6.83 (d, J = 8.2 Hz, 1 H), 6.71 (d, J =
15.9 Hz, 1 H), 6.28–6.15 (m, 1 H), 3.82 (s, 3 H), 2.56–2.15 (m, 2 H),
1.56–1.45 (m, 2 H), 0.95 (t, J = 7.3 Hz, 3 H).
1H NMR (400 MHz, CDCl3):  = 8.49 (d, J = 4.8 Hz, 2 H), 7.19 (d, J = 4.8
Hz, 2 H), 6.51–6.41 (m, 1 H), 6.31 (d, J = 15.9 Hz, 1 H), 2.27–2.16 (m, 2
H), 1.58–1.46 (m, 2 H), 0.96 (t, J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 150.1, 145.4, 136.3, 128.0, 120.8, 35.2,
22.3, 13.8.
13C NMR (100 MHz, CDCl3):  = 156.4, 131.8, 127.9, 127.2, 126.5,
124.5, 120.8, 110.9, 55.6, 35.7, 22.8, 13.9.
These spectroscopic data match those previously reported.17
HRMS (APCI): m/z calcd for C10H14N+ [M + H]+: 148.1121; found:
148.1120.
(E)-2-(Pent-1-en-1-yl)naphthalene (E-1l)
Colorless oil; yield: 52.9 mg (90%); E/Z = 12:1.
(E)-(4,8-Dimethylnona-1,7-dien-1-yl)benzene (E-1q)
Colorless oil; yield: 61.5 mg (90%); E/Z = 8:1.
IR (neat): 2977, 1332, 1371, 1300, 1141, 854 cm–1
.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

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1H NMR (400 MHz, CDCl3):  = 7.37–7.23 (m, 4 H), 7.21–7.16 (m, 1 H),
6.36 (d, J = 15.8 Hz, 1 H), 6.25–6.16 (m, 1 H), 5.11 (t, J = 7.3 Hz, 1 H),
2.29–2.16 (m, 1 H), 2.11–1.92 (m, 4 H), 1.68 (s, 3 H), 1.61 (s, 3 H),
2.29–2.16 (m, 1 H), 1.25–1.15 (m, 1 H), 0.93 (d, J = 6.7 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 141.9, 137.8, 130.5, 130.1, 128.8,
128.6, 128.5, 127.1, 126.1, 126.0, 36.0, 35.0.
These spectroscopic data match those previously reported.22
13C NMR (100 MHz, CDCl3):  = 138.1, 131.3, 131.1, 129.8, 128.6,
126.9, 126.1, 125.0, 40.7, 36.9, 33.1, 25.9, 25.8, 19.7, 17.8.
(E)-1,2-Diphenylethene (E-1w)
White solid; yield: 49.1 mg (91%); E/Z >15:1; mp: 126–127°C.
1H NMR (400 MHz, CDCl3):  = 7.53–7.48 (m, 4 H), 7.38–7.32 (m, 4 H),
7.28–7.21 (m, 2 H), 7.11–7.09 (m, 2 H).
+
HRMS (APCI): m/z calcd for C17H25 [M + H]+: 229.1951; found:
229.1951.
13C NMR (100 MHz, CDCl3):  = 137.5, 128.84, 128.81, 127.8, 126.7.
These spectroscopic data match those previously reported.23
(E)-(7-Chlorohept-1-en-1-yl)benzene (E-1r)
Colorless oil; yield: 56.1 mg (90%); E/Z = 9:1.
1H NMR (400 MHz, CDCl3):  = 7.38–7.25 (m, 4 H), 7.21–7.15 (m, 1 H),
6.38 (d, J = 16.0 Hz, 1 H), 6.24–6.14 (m, 1 H), 3.52 (t, J = 6.7 Hz, 2 H),
2.21 (d, J = 6.1 Hz, 2 H), 1.84–1.72 (m, 2 H), 1.52–1.44 (m, 4 H).
13C NMR (100 MHz, CDCl3):  = 137.9, 130.6, 130.2, 128.6, 127.0,
126.0, 45.1, 32.9, 32.6, 28.7, 26. 6.
(E)-1-Fluoro-4-styrylbenzene (E-1x)
White solid; yield: 53.4 mg (90%); E/Z >15:1; mp: 123–124°C.
1H NMR (400 MHz, CDCl3):  = 7.52–7.44 (m, 4 H), 7.39–7.32 (m, 2 H),
7.29–7.22 (m, 1 H), 7.11–6.97 (m, 4 H).
13C NMR (100 MHz, CDCl3):  = 162.5 (d, J = 247.0 Hz), 137.3, 133.7 (d,
J = 3.5 Hz), 128.9, 128.7 (d, J = 2.3 Hz), 128.1 (d, J = 7.9 Hz), 127.8,
127.6, 126.6, 115.8 (d, J = 21.6 Hz).
These spectroscopic data match those previously reported.20
(E)-(7-Methoxyhept-1-en-1-yl)benzene (E-1s)
Colorless oil; yield: 55.7 mg (91%); E/Z = 12:1.
These spectroscopic data match those previously reported.24
IR (neat): 2929, 2856, 2827, 1120, 964, 744, 692 cm–1
.
(E)-1-Methoxy-4-styrylbenzene (E-1y)
1H NMR (400 MHz, CDCl3):  = 7.35–7.23 (m, 4 H), 7.19–7.13 (m, 1 H),
6.36 (d, J = 15.8 Hz, 1 H), 6.24–6.15 (m, 1 H), 3.35 (t, J = 6.6 Hz, 2 H),
3.31 (s, 3 H), 2.24–2.16 (m, 2 H), 1.63–1.53 (m, 2 H), 1.53–1.43 (m, 2
H), 1.43–1.34 (m, 2 H).
13C NMR (100 MHz, CDCl3):  = 138.0, 131.1, 130.0, 128.6, 126.9,
126.1, 73.0, 58.7, 33.1, 29.7, 29.4, 25.9.
White solid; yield: 57.33 mg (91%); E/Z >15:1; mp: 134–135°C.
1H NMR (400 MHz, CDCl3):  = 7.50–7.23 (m, 4 H), 7.36–7.30 (m, 2 H),
7.25–7.20 (m, 1 H), 7.08–6.94 (m, 2 H), 6.89 (d, J = 7.6 Hz, 2 H), 3.81 (s,
3 H).
13C NMR (100 MHz, CDCl3):  = 159.3, 137.7, 130.2, 128.7, 128.2,
127.8, 127.2, 126.7, 126.3, 114.2, 55.4.
HRMS (APCI): m/z calcd for C14H21O+ [M + H]+: 205.1587; found:
205.1587.
These spectroscopic data match those previously reported.24
(E)-1-Styryl-4-(trifluoromethyl)benzene (E-1z)
(E)-2-[(7-Phenylhept-6-en-1-yl)oxy]tetrahydro-2H-pyran (E-1t)
Colorless oil; yield: 73.9 mg (90%); E/Z = 12:1.
White solid; yield: 66.23 mg (91%); E/Z >15:1; mp: 132–134°C.
1H NMR (400 MHz, CDCl3) :  = 7.62–7.59 (m, 4 H), 7.56–7.51 (m, 2 H),
7.41–7.35 (m, 2 H), 7.33–7.27 (m, 1 H), 7.16 (q, J = 16.4 Hz, 2 H).
13C NMR (100 MHz, CDCl3) :  = 141.0, 136.89, 131.4, 129.6, 129.3,
129.0, 128.4, 127.3, 127.0, 126.7, 125.78 (q, J = 3.7 Hz).
These spectroscopic data match those previously reported.25
IR (neat): 2954, 2923, 2852, 1656, 1633, 1120, 1078, 1033 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.36–7.26 (m, 4 H), 7.22–7.14 (m, 1 H),
6.38 (d, J = 15.8 Hz, 1 H), 6.31–6.13 (m, 1 H), 4.60–4.55 (m, 1 H), 3.87
(t, J = 9.3 Hz, 1 H), 3.81–3.69 (m, 1 H), 3.56–3.45 (m, 1 H), 3.44–3.34
(m, 1 H), 2.28–2.16 (m, 2 H), 1.91–1.78 (m, 1 H), 1.73–1.41 (m, 11 H).
13C NMR (100 MHz, CDCl3):  = 138.0, 131.1, 130.0, 128.6, 126.9,
126.0, 99.0, 67.7, 62.5, 33.1, 30.9, 29.8, 29.3, 26.0, 25.6, 19.8.
(E)-1,3-Difluoro-5-styrylbenzene (E-1aa)
+
HRMS (APCI): m/z calcd for C18H27O2 [M + H]+: 275.2006; found:
275.2006.
White solid; yield: 57.33 mg (91%); E/Z >15:1; mp: 132–133°C.
1H NMR (400 MHz, CDCl3):  = 7.53–7.47 (m, 2 H), 7.41–7.34 (m, 2 H),
7.32–7.27 (m, 1 H), 7.13–6.95 (m, 4 H), 6.72–6.65 (m, 1 H).
13C NMR (100 MHz, CDCl3):  = 164.67 (d, J = 13.2 Hz), 162.21 (d, J =
13.1 Hz), 140.93 (t, J = 9.5 Hz), 136.48, 131.44, 128.53, 127.94 (d, J =
202.1 Hz), 126.66, 109.18 (d, J = 6.0 Hz), 102.85 (t, J = 25.7 Hz).
(E)-(4-Methylpent-1-en-1-yl)benzene (E-1u)
Colorless oil; yield: 43.1 mg (90%); E/Z = 13:1.
1H NMR (400 MHz, CDCl3):  = 7.37–7.32 (m, 2 H), 7.32–7.25 (m, 2 H),
7.21–7.14 (m, 1 H), 6.36 (d, J = 15.8 Hz, 1 H), 6.26–6.17 (m, 1 H), 2.12–
2.06 (m, 2 H), 1.79–1.67 (m, 1 H), 0.94 (d, J = 6.7 Hz, 6 H).
These spectroscopic data match those previously reported.26
13C NMR (100 MHz, CDCl3):  = 138.1, 131.0, 130.0, 128.6, 126.9,
(E)-1-(4-Styrylphenyl)propan-1-one (E-1ab)
126.1, 42.6, 28.8, 22.5.
White solid; yield: 63.7 mg (90%); E/Z >15:1; mp: 129–130°C.
These spectroscopic data match those previously reported.21
1H NMR (400 MHz, CDCl3):  = 7.96 (d, J = 8.0 Hz, 2 H), 7.58 (d, J = 8.1
Hz, 2 H), 7.54 (d, J = 7.7 Hz, 2 H), 7.40–7.28 (m, 3 H), 7.22 (d, J = 16.4
Hz, 1 H), 7.13 (d, J = 16.3 Hz, 1 H), 3.00 (q, J = 7.3 Hz, 2 H), 1.24 (t, J =
7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 200.3, 141.9, 136.9, 135.9, 131.4,
128.9, 128.7, 128.4, 127.7, 126.9, 126.6, 31.9, 8.5.
(E)-Prop-1-ene-1,3-diyldibenzene (E-1v)
Colorless oil; yield: 52.9 mg (91%); E/Z = 11:1.
1H NMR (400 MHz, CDCl3):  = 7.38–7.23 (m, 6 H), 7.23–7.15 (m, 4 H),
6.40 (d, J = 15.8 Hz, 1 H), 6.29–6.19 (m, 1 H), 2.77 (t, J = 7.7 Hz, 2 H),
2.56–2.47 (m, 2 H).
These spectroscopic data match those previously reported.27
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

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H. Yang et al.
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Synthesis
(E)-4-Styrylphenyl Pivalate (E-1ac)
Supporting Information
White solid; yield: 73.8 mg (88%); E/Z >15:1; mp: 157–159°C.
1H NMR (400 MHz, CDCl3):  = 7.50 (d, J = 7.9 Hz, 4 H), 7.35 (t, J = 7.6
Hz, 2 H), 7.28–7.21 (m, 1 H), 7.08–7.02 (m, 4 H), 1.36 (s, 9 H).
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707166.
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13C NMR (100 MHz, CDCl3):  = 177.2, 150.7, 137.3, 135.0, 128.9,
References
128.8, 127.9, 127.8, 127.5, 126.6, 121.9, 39.2, 27.3.
These spectroscopic data match those previously reported.28
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borolane (2a)
Colorless oil; yield: 48.5 mg (55%).
1H NMR (400 MHz, CDCl3):  = 7.36–7.29 (m, 4 H), 7.28–7.19 (m, 2 H),
2.33–2.27 (t, J = 7.8 Hz, 2 H), 1.51–1.40 (m, 2 H), 1.25 (s, 12 H), 0.87 (t,
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13C NMR (100 MHz, CDCl3):  = 142.0, 138.1, 129.1, 128.2, 127.1, 83.5,
31.7, 24.9, 23.4, 14.4. The carbon signal attached to B atom was not
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These spectroscopic data match those previously reported.29
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(E)-1-(4-Ethoxystyryl)-3,5-dimethoxybenzene (E-3)
To a suspension of 4-ethoxybenzyltriphenylphosphonium bromide
(10 mmol, 1.0 equiv) in THF (30 mL) were added n-BuLi (1.2 equiv) at
–78 °C, and the mixture was stirred at r.t. for 3 h. Then, 3,5-di-
methoxybenzaldehyde (10 mmol) was added and the solution was
stirred for 5 h. The resulting mixture was quenched with sat. aq NH4Cl
and extracted with EtOAc. The combined organic layers were dried
(anhyd Na2SO4) and concentrated under reduced pressure. The resi-
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ford 3 as a stereoisomeric mixture.
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In a N2-filled glovebox, to an oven-dried vial were charged with
[Rh(cod)Cl]2 (4.5 mg, 0.009 mmol), Xantphos (15.6 mg, 0.027 mmol)
and DME (0.5 mL). After stirring for 20 min at r.t., B2pin2 (3.8 mg, 0.05
equiv) was added and the resulting mixture was stirred for an addi-
tional 10 min at r.t. Next, the above prepared 3 (85.2 mg, 0.3 mmol)
was added by a syringe and followed by the addition of DME (0.5 mL).
The vial, sealed with a Teflon-lined cap, was removed out from the
glovebox and stirred at 60 °C. The reaction mixture was filtered
through Celite and washed with DCM. The solvent was removed and
the residue was purified by silica gel chromatography using petro-
leum ether as the eluent to afford E-3; yield: 74.1 mg (86%).
1H NMR (400 MHz, CDCl3):  = 7.42 (d, J = 8.7 Hz, 2 H), 7.06–7.00 (m, 1
H), 6.93–6.84 (m, 3 H), 6.64 (d, J = 2.2 Hz, 2 H), 6.37 (s, 1 H), 4.02 (q, J =
7.0 Hz, 2 H), 3.80 (s, 6 H), 1.40 (t, J = 7.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 161.1, 158.9, 139.9, 129.9, 128.9,
127.9, 126.6, 114.8, 104.4, 99.7, 63.6, 55.4, 14.9.
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135, 3327. (l) Larsen, C. R.; Erdogan, G.; Grotjahn, D. B. J. Am.
Chem. Soc. 2014, 136, 1226. (m) Trost, B. M.; Cregg, J. J.; Quach,
N. J. Am. Chem. Soc. 2017, 139, 5133. (n) Paulson, E. R.; Moore, C.
E.; Rheingold, A. L.; Pullman, D. P.; Sindewald, R. W.; Cooksy, A.
L.; Grotjahn, D. B. ACS Catal. 2019, 9, 7217. (o) Larsen, C. R.;
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Yamagata, T.; Akutagawa, S.; Kumobayashi, H.; Taketomi, T.;
The data are in accordance with the literature.8b
Funding Information
Financial supports from the National Natural Science Foundation of
China (Grant No. 21702056, 21971059 and 21901068), the National
Program for Thousand Young Talents of China, and the Fundamental
Research Funds for the Central Universities are greatly appreciated.
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© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H

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© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–H