Pd-Catalyzed Cross-Coupling of Organostibines with Styrenes to Give Unsymmetric (E)-Stilbenes and (1 E,3 E)-1,4-Diarylbuta-1,3-dienes and Fluorescence Properties of the Products

Article abstract of DOI:10.1021/acs.orglett.1c01532

A general and effective palladium-catalyzed cross-coupling of organostibines with styrenes to give (E)-olefins was disclosed. By the use of an organostibine reagent, this method can produce unsymmetric (E)-1,2-diarylethylenes and (1E,3E)-1,4-diarylbuta-1,3-dienes in good yields with high E/Z selectivity and good functional group tolerance. Resveratrol and DMU-212 were synthesized in high yield. The protocol can be extended to the synthesis of (1E,3E,5E)-1,6-diphenylhexa-1,3,5-triene in 40% yield. Products 5e, 5f, and 7a showed good photoluminescence quantum yields ranging from 72 to 99%.

Full text of DOI:10.1021/acs.orglett.1c01532

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Letter
Pd-Catalyzed Cross-Coupling of Organostibines with Styrenes to
Give Unsymmetric (E)‑Stilbenes and (1E,3E)‑1,4-Diarylbuta-1,3-
dienes and Fluorescence Properties of the Products
Zhao Zhang, Dejiang Zhang, Longzhi Zhu, Dishu Zeng, Nobuaki Kambe, and Renhua Qiu*
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ABSTRACT: A general and effective palladium-catalyzed cross-
coupling of organostibines with styrenes to give (E)-olefins was
disclosed. By the use of an organostibine reagent, this method can
produce unsymmetric (E)-1,2-diarylethylenes and (1E,3E)-1,4-
diarylbuta-1,3-dienes in good yields with high E/Z selectivity and
good functional group tolerance. Resveratrol and DMU-212 were
synthesized in high yield. The protocol can be extended to the
synthesis of (1E,3E,5E)-1,6-diphenylhexa-1,3,5-triene in 40% yield.
Products 5e, 5f, and 7a showed good photoluminescence quantum
yields ranging from 72 to 99%.
nsymmetric (E)-stilbenes and related conjugated π-
Because of their wide application in many fields, the
synthesis of unsymmetric (E)-stilbene-like olefins has attracted
much attention in organic synthesis. A variety of powerful
methods have been disclosed.7 Among them, the transition-
metal-catalyzed Heck coupling reaction is one of the most
powerful tools for the formation of (E)-olefins,8 especially for
the synthesis of (E)-1,2-diarylethylenes. Excellent examples
based on catalysis by Pd,7a,9 Ni,10 and Cu1b with aryl halides or
arylboronic acids have been developed, as shown in Scheme
1a. Compared with the well-established methodologies for
unsymmetric (E)-1,2-diarylethylenes, the synthesis of unsym-
metric (1E,3E)-1,4-diarylbuta-1,3-dienes (Scheme 1b) is quite
rare. Recently three examples demonstrated the synthesis of
the above molecules. Kamigata et al.11 disclosed the first
example of Ru(PPh3)Cl3-catalyzed Heck coupling of alkene-
sulfonyl chlorides with styrenes, which gave higher yields of
(1E,3E)-1,4-diarylbuta-1,3-dienes at 150 °C. Xu et al.12 also
successfully realized the Heck reaction between olefins and β-
bromostyrene using a μ-OMs palladium dimer complex as the
catalyst with the yield of 82%. Miura et al.13 also disclosed a
palladium-catalyzed coupling reaction of cinnamic acid with 1-
bromostyrene. Besides common Heck coupling products, their
protocol realized the synthesis of (1E,3E)-1,4-diarylbuta-1,3-
dienes and (1E,3E,5E)-1,6-diarylhexa-1,3,5-trienes (Scheme
1c).
U
electron compounds are widely used in materials,
medicine and health, cosmetics, and other important fields.1−6
As shown in Figure 1, resveratrol (A), an example of an (E)-
Figure 1. Representative (E)-stilbene-like olefins.
1,2-diarylethylene, can be used as a dietary supplement and has
been observed to have chemoprophylaxis and cytoinhibitory
effects on a variety of human tumor cell lines.2 DMU-212 (B),
which is also an (E)-1,2-diarylethylene, has been demonstrated
to possess cytotoxic activity in ovarian, breast, and colorectal
cancer cell lines.3 In addition, unsymmetric conjugated
polyolefins, such as (1E,3E)-1,4-diarylbuta-1,3-diene and
(1E,3E,5E)-1,6-diarylhexa-1,3,5-triene, which exhibit good
fluorescence properties, are of great value in the fields of
optical functional materials, liquid crystals, and luminescent
materials.4 For example, conjugated dienes C and D with
electron-withdrawing cyanide and nitro groups have good
fluorescent probe properties,5 while the conjugated trienes E
and F can be used as fluorescent probes of lipid membranes for
cancer research.6
Received: May 5, 2021
Published: June 7, 2021
https://doi.org/10.1021/acs.orglett.1c01532
© 2021 American Chemical Society
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a
Scheme 1. Strategy for Unsymmetric (E)-Stilbene-like
Olefins
Table 1. Screening of the Reaction Conditions
a
1a (0.1 mmol), 2a (0.15 mmol), Pd catalyst (0.01 mmol), and the
base (0.2 mmol) in the solvent (2.0 mL) with the oxidant (1.0−2.0
We are interested in organoantimony chemistry14 and
olefins.15 Organoantimony reagents have been used for the
Heck coupling by several groups for years. In 2020, Yasuike et
al. disclosed a Pd-catalyzed oxidative Heck-type arylation of
vinyl ketones, alkenes, and acrylates with Sb-aryltetrahydrodi-
benz[c,f ][1,5]azastibocines, which is an important step
forward in organoantimony chemistry.14b However, this
protocol failed to efficiently produce (E)-1,2-diphenylethylene
(52% yield). Very recently, by simple modification of the N-
substitution group from tert-butyl to phenyl on the
tetrahydrodibenz[c,f ][1,5]azastibocines, we established an
efficient protocol toward biaryls via Pd-catalyzed oxidative
cross-coupling of arylated organostibines with arylboronic
acids.14c
equiv) and H2O (60−100 μL) at 100 °C in air for 2 h in a sealed
b
c
d
tube. GC yields are shown. Under N2. Without Cu(OAc)2. Under
N2 and without Cu(OAc)2.
Table 2 shows the isolated yields of (E)-olefins 3a−u
obtained by the Pd-catalyzed Heck coupling of substituted
Table 2. Substrate Scope of Olefins for Unsymmetric (E)-
a
1,2-Diarylethylenes
In the present work, we used 6-phenyl-12-aryl-5,6,7,12-
tetrahydrodibenzo[c,f][1,5]azastibocines as coupling reagents
to react with styrenes, which can yield unsymmetric (E)-
stilbene-like olefins with high efficiency and regioselectivity.
This method can produce not only unsymmetric (E)-1,2-
diarylethylenes in good yields but also unsymmetric (1E,3E)-
1,4-diarylbuta-1,3-dienes (Scheme 1d). Furthermore, this
procedure can also be extended to produce (1E,3E,5E)-1,6-
diphenylhexa-1,3,5-triene in satisfactory yield with good
regioselectivity. This is the first example of an oxidative
Mizoroki−Heck reaction using organostibine reagents to react
with olefins for the synthesis of unsymmetric (1E,3E)-1,4-
diarylbuta-1,3-dienes.
As shown in Table 1, we initially conducted the screening
for the Heck coupling with 6,12-diphenyl-5,6,7,12-
tetrahydrodibenzo[c,f ][1,5]azastibocine (1a) and styrene
(2a). We found that the ligand did not affect the reaction
(see Table S2) and that the addition of Cu(OAc)2 as an
oxidant greatly improved the reaction efficiency (entries 1−3).
Adding 100 μL of water increased the yield of 3a to 85% (entry
6), which may be due to coordination of the water molecule to
antimony, lowering the reaction activation energy (see Figure
S4).16 Then the solvent and the amount of oxidant were
screened (entries 7−12). DMF was found to be the best
solvent, and 1.5 equiv of Cu(OAc)2 was enough to oxidize the
reaction. Pd(OAc)2 was the best catalyst under an air
atmosphere, giving 3a in 95% GC yield (entry 11), while the
use of a nitrogen atmosphere lowered the yield of 3a to 68%,
indicating that the oxygen may also work as an oxidant to some
extent (entries 13−15). All entries gave only a trace amount of
3a′ derived from homocoupling of 1a, indicating the advantage
of organoantimony reagents.
a
1a (0.1 mmol), 2 (0.15 mmol), Pd(OAc)2 (10 mol %), NaHCO3
(0.2 mmol), and Cu(OAc)2 (0.2 mmol) in 2.0 mL of DMF at 100 °C
for 8 h. Isolated yields of 3 are shown. E:Z ratios are given in
parentheses and were determined by H NMR analysis of the crude
mixtures.
1
styrenes 2 with 1a. Good functional group tolerance was
observed, as a variety of groups, such as Bu, Me, NO2, CF3,
t
CN, F, Cl, pyridine, sulfone, and ester, are well-tolerated in this
protocol. The expected stilbene derivatives 3a−h, 3j, 3k, and
3p were obtained by reaction with substituted styrenes in good
yields (>75%) with excellent regioselectivity (E:Z > 99:1). The
reaction is also compatible with halogenated olefins (X = F,
Cl) but poor for bromostyrene and iodostyrene, which may
due to side reactions of the active C−Br/C−I bonds of the
halides. Meanwhile, because of the steric hindrance effect, the
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yields of 3i and 3o were lower (41% and 44%, respectively),
but the regioselectivity still remained the same as for 3a−i. For
other olefins apart from styrenes, the corresponding products
3q−u were also obtained in moderate to good yields with E:Z
> 99:1.
Then a series of Sb-aryl organostibines with the
tetrahydrodibenz[c,f ][1,5]azastibocine framework were syn-
thesized and subjected to reaction with styrene in this reaction
system (4a−p; Table 3). Alkyl and aryl substituents were
Table 3. Substrate Scope of Sb-Aryl Organostibines for
a
Unsymmetric (E)-1,2-Diarylethylenes
butadienes. After investigating the reaction conditions, we
found that ligands were needed to inhibit the generation of
homocoupling products. Screening of a series of ligands
showed that 1,10-phenanthroline (1,10-Phen) was the best
ligand to improve the reaction effect (see Table S8).
Table 4 shows the results of the catalytic reaction of 1b with
various aromatic olefins. It shows a wide substrate scope
Table 4. Substrate Scope of Stilbenes for Unsymmetric
a
(1E,3E)-1,4-Diarylbuta-1,3-dienes
a
1 (0.1 mmol), 2a (0.15 mmol), Pd(OAc)2 (10 mol %), NaHCO3
(0.2 mmol), and Cu(OAc)2 (0.2 mmol) in 2.0 mL of DMF at 100 °C
for 8 h. Isolated yields of 4 are shown. E:Z ratios are given in
1
parentheses and were determined by H NMR analysis of the crude
mixtures.
tolerated in the system with good yields and regioselectivity.
Various organostibines can achieve satisfactory yields, such as
4-methyl (4b, 95%), 4-n-butyl (4e, 86%), 4-methoxy (4f,
74%), 3-CF3 (4j, 93%), and 4-Ph (4m, 64%). A cyano group
afforded a modest 30% yield of 4l in the catalytic reaction
system, while some strong electron-withdrawing functional
groups cannot be tolerated, such as ester, nitro, bromine, and
other functional groups. We compared the yields of the
methyl-substituted products (4b−d) and found that the yield
decreased in the order 4b > 4c > 4d, indicating steric
hindrance of the reaction, with the meta position giving relative
lower regioselectivity. Heteroatom-containing groups could
also survive in this transformation, generating the correspond-
ing products 4o and 4p in good yields with >99% E/Z
selectivity.
It has been reported that polyphenols and methyl ether
derivatives have possible anticancer activity,17 among which
resveratrol and DMU-212 are two compounds that have been
studied extensively.2b,18 By means of the developed method,
DMU-212 and resveratrol were prepared via a single-step or
two-step procedure, respectively, in yields of 65% (4q) and
60% (4s) (eqs 1 and 2).
a
1b (0.1 mmol), 2 (0.15 mmol), Pd(OAc)2 (10 mol %), NaHCO3
(0.2 mmol), Cu(OAc)2 (0.15 mmol), and 30 mol % 1,10-Phen in 2.0
mL of DMSO at 100 °C for 8 h. Isolated yields of the main products 5
and GC yields of 5′ and 5″ are shown. The ratios of EE isomers are
given in parentheses and were estimated from the areas in GC and
GC−MS of the crude mixtures.
toward to both electron-donating groups and electron-
withdrawing groups in good yields (5a-l). The reaction
exhibits different dependences on the electronic effect and
spatial effect with respect to electron-donating groups and
electron-withdrawing groups. When an electron-withdrawing
group (CF3) was attached at the para and meta position of the
aromatic olefin, the yield was increased from 69% (5h) to 91%
(5g). When an electron-donating methyl group was attached at
the same position, almost the same yields were observed (85%
for 5a and 88% for 5b).
Table 5 shows the use of 1-phenyl-1,3-butadiene as the
substrate to synthesize conjugated dienes through the oxidative
Heck coupling method. The reaction is compatible with a
variety of substituted organostibine compounds, and all of the
products were unsymmetric (1E,3E)-1,4-diarylbuta-1,3-dienes
It was found that the reaction of 1b with aromatic olefins
provided conjugated dienes in low yields with poor selectivity,
which inspired us to focus on the synthesis of 1,4-diaryl-1,3-
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72% to 99%, except for 6c and 6g. These primary results
indicate that these polyolefins may have potential for use in the
area of biochemistry.
Table 5. Substrate Scope of Sb-Aryl Organostibines for
(1E,3E)-1,4-Diarylbuta-1,3-dienes
a
We began to investigate the yield of 3a and 3a′ in the Heck
reaction over time, and the simulated curve is shown in Figure
S3. The yield of the oxidative Heck coupling product 3a
increased smoothly to 95% within 2 h, and the byproduct 3a′
reached a maximum yield of 2% at only 20 min. On the basis of
the previously reported literature14b,19 and the control
experiments, a possible catalytic cycle for the reaction of
organostibine compounds with olefins is proposed as shown in
Scheme 2. First, organostibine compound 1b reacts with
Scheme 2. Proposed Mechanism
a
1 (0.1 mmol), 6a (0.15 mmol), Pd(OAc)2 (10 mol %), DMF (2.0
mL), NaHCO3 (0.2 mmol), 1,10-Phen (30 mol %) and Cu(OAc)2
(0.2 mmol) at 100 °C in air for 8 h. Isolated yields of the main
products 5 and 6 are shown. The ratios of EE isomers are given in
parentheses and were estimated from the areas in GC and GC−MS of
the crude mixtures.
Pd(II) to produce organic palladium intermediate I, which can
react with olefin 2 to give intermediate II as a fast path as cycle
A. Then β-H elimination from intermediate II occurs, giving
the desired product 5 and a Pd(0) species. Finally, the Pd(0)
species can be oxidized to the active Pd(II) intermediate in the
presence of Cu(II)/O2 to finish the catalytic cycle. However,
there could be another route for homocoupling of 1b, shown
as cycle B, in which intermediate I could react with 1b to
generate intermediate III as a slow path. III would then
undergo reductive elimination to give Pd(0) and the side
product 5′ (Table 4).
(5c, 5e, 5l, 5g, 6a−g) and were obtained in good yields with
excellent regioselectivity (EE:ZE > 99:1).
Furthermore, we synthesized hexatriene 7a in 40% yield
under the standard conditions by regulation of the palladium
catalyst and base, as shown in eq 3. Further research on
conjugated polyenes such as conjugated trienes and tetraenes is
underway in our laboratory.
In summary, we have developed a new methodology for the
formation of conjugated dienes via oxidative cross-coupling of
organostibine compounds with olefins. The breaking of the
Sb−C bond provides a good opportunity for the formation of
unsymmetric stilbenes and conjugated dienes. The reaction
system has good tolerance to olefin functional groups,
including methoxy, fluorine, trifluoromethyl, ester, nitro,
naphthalene ring, trimethylsilane, and ether groups. For
organostibine compounds, electron-donating functional groups
have achieved good yields. This reaction system provides
potential value for the utilization of organostibine compounds
and also provides a strategy for the generation of unsymmetric
stilbenes and conjugated dienes.
Conjugated polyolefins have been demonstrated to have the
potential in biochemistry because of their excellent fluo-
rescence ability. We thus investigated the photophysical
properties of selected examples of the obtained 1,3-dienes
and 1,3,5-trienes (Figure 2). The UV−vis absorption and
ASSOCIATED CONTENT
* Supporting Information
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The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c01532.
Figure 2. (A) UV−vis absorption and (B) fluorescence emission
spectra of selected examples of 1,3-dienes and 1,3,5-trienes.
Detailed experimental procedures, characterization data,
1
and copies of the H, 19F, and 13C NMR spectra of the
obtained products (PDF)
FAIR data, including the primary NMR FID files, for
compounds 3a−u, 4a−s, 5a−l, 6a−g, and 7a (ZIP)
fluorescence emission spectra and the photoluminescence
quantum yields (PLQYs) in toluene were acquired. The UV−
vis absorption and fluorescence emission bands of 1,3,5-triene
7a are bathochromically shifted compared with those of the
dienes (5e, 5f, 6e−g) as a result of the enhanced conjugation.
Besides, these compounds showed good PLQYs ranging from
Accession Codes
CCDC 2065213 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
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via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, U.K.; fax: +44 1223 336033.
Wong (The Hong Kong Polytechnic University) for helpful
discussions.
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AUTHOR INFORMATION
■
Corresponding Author
Renhua Qiu − State Key Laboratory of Chemo/Biosensing
and Chemometrics, Advanced Catalytic Engineering Research
Center of the Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082,
P. R. China; Shenzhen Research Institute, Hunan University,
Shenzhen 518000, P. R. China; orcid.org/0000-0002-
8423-9988; Email: renhuaqiu1@hnu.edu.cn
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Authors
Zhao Zhang − State Key Laboratory of Chemo/Biosensing
and Chemometrics, Advanced Catalytic Engineering Research
Center of the Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082,
P. R. China
Dejiang Zhang − State Key Laboratory of Chemo/Biosensing
and Chemometrics, Advanced Catalytic Engineering Research
Center of the Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082,
P. R. China
Longzhi Zhu − State Key Laboratory of Chemo/Biosensing
and Chemometrics, Advanced Catalytic Engineering Research
Center of the Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082,
P. R. China; Center for Biomedical Optics and Photonics
(CBOP) and College of Physics and Optoelectronic
Engineering, Key Laboratory of Optoelectronic Devices and
Systems, Shenzhen University, Shenzhen 518060, P. R.
China; orcid.org/0000-0001-5161-9944
Dishu Zeng − State Key Laboratory of Chemo/Biosensing and
Chemometrics, Advanced Catalytic Engineering Research
Center of the Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082,
P. R. China
Nobuaki Kambe − State Key Laboratory of Chemo/
Biosensing and Chemometrics, Advanced Catalytic
Engineering Research Center of the Ministry of Education,
College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, P. R. China; The Institute of
Scientific and Industrial Research, Osaka University, Ibaraki,
Osaka 567-0047, Japan
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Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01532
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank the National Natural Science Foundation of
China (21676076, 21878071, and 21971060), the Hu-Xiang
High Talent Project in Hunan Province (2018RS3042), the
Recruitment Program for Foreign Experts of China
(WQ20164300353), and the Natural Science Foundation of
Changsha (kq2004008) for financial support. R.Q. thanks Prof.
Shuang-Feng Yin (Hunan University) and Prof. Wai-Yeung
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