Novel π-expanded chrysene-based axially chiral molecules: 1,1′-bichrysene-2,2′-diols and thiophene analogs

Article abstract of DOI:10.1177/1747519820914837

1,1′-Bichrysene-2,2′-diol and its thiophene analogs, 6,6′-biphenanthro-[1,2-b]thiophene-7,7′-diols, as a series of novel π-expanded chrysene-/phenanthro[1,2-b]thiophene-based axially chiral molecules are synthesized from 1,1′-bi-2-naphthols with key steps

Full text of DOI:10.1177/1747519820914837

9
research-arti
1cle2020 4837CHL0010.1177/1747519820914837Journal of Chemical ResearchAn et al.
Research Paper
Journal of Chemical Research
–5
1
Novel π-expanded chrysene-based axially chiral
molecules: 1,1′-bichrysene-2,2′-diols
and thiophene analogs
© The Author(s) 2020
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Shujie An, Guofeng Tang, Yaling Zhong, Li Ma and Qiancai Liu
Abstract
1,1′-Bichrysene-2,2′-diol and its thiophene analogs, 6,6′-biphenanthro-[1,2-b]thiophene-7,7′-diols, as a series of novel π-
expanded chrysene-/phenanthro[1,2-b]thiophene-based axially chiral molecules are synthesized from 1,1′-bi-2-naphthols
with key steps including a Suzuki coupling, a Wittig reaction, and acid-mediated cyclization.
Keywords
π-expanded, chrysene, oxidative coupling, synthesis, thiophene
Date received: 7 January 2020; accepted: 3 March 2020
(ChemBioDraw version 13.0)
Thiophene and its analogs are often regarded as elec-
Introduction
1
2
tron-donating moieties in materials chemistry. It was
found that the electron transfer among molecules and the
antioxidative capacity of compounds could both be
Due to the superior electronic and optical properties,
1,1′-bi-2-naphthol (BINOL) and other axially binaphthol-
related chiral molecules have recently been widely
13
improved by fusing thiophene onto PAHs.
1
–3
studied. The functionalities of BINOL and their deriva-
tives can be tuned through the expansion of their π-system
and by chemical modifications at specific sites. Among Results and discussion
them, the expansion of the π-system is the most common
As a part of our ongoing research on heterocycle-fused
4
method to date. Large π-extended polycyclic aromatic
binaphthalenes and binaphthols (BINOLs), we have
extended our interest on BINOL analogs using chrysene
and phenanthro[1,2-b]thiophene as replacements for the
naphthalene motifs. It was reported that pyrene-based
BINOLs can lead to a broader application of π-expanded
5
6
hydrocarbons (PAHs) such as anthracene, phenanthrene,
7
8
pyrene, and naphtho[2,3-b]furans, as replacements of the
naphthalene rings of BINOL, could increase the rotational
isomeric space through larger dihedral angles (Figure 1).
Other advantages of such replacements to be addressed are
reduced molecular energy and stable molecular structure,
higher luminescence efficiency and extended fluorescence
lifetime, and so on. These advantages lead to numerous University, Shanghai, P.R. China
School of Chemistry and Molecular Engineering, East China Normal
9
applications of PAH-type BINOLs in the areas of circularly
Corresponding author:
polarized luminescence (CPL) spectroscopy and as starting
Qiancai Liu, School of Chemistry and Molecular Engineering, East China
Normal University, 500 Dongchuan Road, Shanghai 200241, P.R. China.
Email: qcliu@chem.ecnu.edu.cn
1
0
materials for the preparation of graphene nanoribbons and
11
complex polyarene architectures.

2
Journal of Chemical Research 00(0)
7
axially chiral molecules. Generally, racemic BINOLs and followed by protection of the hydroxy groups with MeI in
their chiral analogs can be synthesized by the oxidation of the presence of K CO in acetone. The palladium-cata-
2
3
β-naphthol with often-used catalysts such as FeCl or lyzed borylation of (S)-/(R)-/(±)-2 with bis(pinacolato)
3
1
4
Cu(OH)Cl·TMEDA. In our case, 2-chrysenol and related diboron was employed to afford the key intermediates,
analogs were very difficult to prepare through simple syn- 6,6′-diboro-2,2′-dimethoxy-1,1′-binaphthalenes [(S)-/(R)-/
thetic strategies, and therefore we thought that it would be (±)-3].
possible to use commercial BINOLs as starting materials
through well-defined and facile synthetic protocols in prepare (S)-/(R)-/(±)-4 via Suzuki coupling with 2-bro-
order to prepare the target molecules (Scheme 1). BINOL mobenzaldehyde at 90°C in a mixture of dioxane and H O
With (S)-/(R)-/(±)-3 in hand, we initially attempted to
2
was functionalized as the dibromide in order to avoid (2:1). The reactions proceeded quite smoothly with isolated
any uncertainty in subsequent steps. 6,6′-Dibromo-2,2′- yields of (S)-/(R)-/(±)-4 up to 73%. When 2-bromo-3-thio-
dimethoxy-1,1′-binaphthalenes [(S)-/(R)-/(±)-2] were phenecarboxaldehyde was used, products (S)-/(R)-/(±)-8
thus obtained by bromination of (S)-/(R)-/(±)-BINOL, were obtained in yields ranging from 70% to 92%.
Next, the Wittig olefinations were applied to (S)-/(R)-/(±)-
4
or -8 with (methoxymethyl)triphenylphosphonium chloride
as the ylide precursor to construct (S)-/(R)-/(±)-5 (E/Z ca. 3:1
1
according to H NMR from crude mixture) and (S)-/(R)-/
1
(
±)-9 (E/Z ca. 4:1 according to H NMR from crude mixture),
which were treated with TfOH to form (S)-/(R)-/(±)-6 and
10 via dehydrative cycloaromatization. Finally, deprotection
-
with BBr was accomplished in dichloromethane at low tem-
3
perature to afford (S)-/(R)-/(±)-1,1′-bichrysene-2,2′-diol
[
(S)-/(R)-/(±)-7] and (S)-/(R)-/(±)-6,6′-biphenanthro[1,2-b]
thiophene-7,7′-diol [(S)-/(R)-/(±)-11].
Conclusion
In conclusion, a facile and atom-economic method for the
synthesisof1,1′-bichrysene-2,2′-dioland6,6′-biphenanthro-
[1,2-b]-thiophene-7,7′-diols has been presented. This
method should also be applicable for the syntheses of dif-
ferent polycyclic aromatics such as polyarenes and nanog-
raphenes. Furthermore, the target molecules could
contribute to molecular recognition and the further explora-
tion of new π-expanded axially chiral molecules. Further
Figure 1. Comparison of axially chiral molecular structures
5
6
7
based on anthracene, phenanthrene, pyrene, and naphtho[2,3-
8
b]furans and those of our work.
Br
Br
Br
O
O
O
O
B
B
Br
2
MeI/K2CO3
acetone
HO
HO
HO
HO
O
O
CH
2
Cl
2
, -78 oC to rt
99%
2
PdCl (dppf)
46%-59%
68%-95%
>
Br
O
(
S)-/(R)-/(±)-BINOL
(S)-/(R)-/(±)-1
(S)-/(R)-/(±)-2
O
O
OMe
Cl
P
Br
O
O
O
O
TfOH
HFIP
O
O
BBr3
HO
HO
CsF, PdCl
dioxane/H
43%-73%
2
(dppf)
2
O
n-BuLi
8%-56%
CH2Cl2
2
O
B
O
O
O
O
O
(S)-/(R)-/(±)-4
(S)-/(R)-/(±)-5
E:Z = ca. 3:1
(S)-/(R)-/(±)-6
(S)-/(R)-/(±)-7
O
42%-70% (2 steps)
B
O
O
O
OMe
S
Cl
Br
O
P
S
S
S
S
S
S
S
S
O
TfOH
HFIP
O
BBr3
HO
HO
(
S)-/(R)-/(±)-3
O
O
O
O
CsF, PdCl
dioxane/H
0%-92%
2
(dppf)
CH2Cl2
n-BuLi
2
O
45%-78%
7
O
O
(S)-/(R)-/(±)-8
(S)-/(R)-/(±)-9
E:Z = ca. 4:1
(S)-/(R)-/(±)-10
(S)-/(R)-/(±)-11
40%-89% (2 steps)
Scheme 1. Synthetic approach toward the target molecules.

An et al.
3
studies on applications of the described molecules are now
in progress in our laboratory.
14.87, 56.87; MS (EI): m/z [M]+ calcd for C H O :
36 26 4
1
5
22.18; found: 522.
(
R)-4: White solid (1.59g, 43%); R =0.47 (PE/EtOAc,
f
1
3
:1); m.p. 138.1–142.8°C; H NMR (500MHz, CDCl ):
3
Experimental
δ=10.10 (s, 2H), 8.09–8.05 (m, 4H), 7.89 (d, J=1.7Hz,
All chemicals were commercially available as analytical or 2H), 7.67 (td, J=7.5, 1.5Hz, 2H), 7.60–7.50 (m, 6H), 7.33
chemical grade. Solvents were purified via standard meth- (dd, J=8.7, 1.9Hz, 2H), 7.27 (d, J=8.8Hz, 2H), 3.87 (s,
1
3
ods before use. All reactions sensitive to air or water were 6H); C NMR (125MHz, CDCl ): δ=192.77, 155.64,
3
conducted under an Ar or N atmosphere. Reactions were 146.07, 133.89, 133.54, 133.37, 132.75, 130.98, 129.96,
2
monitored by thin-layer chromatography (TLC). Silica gel 129.76, 128.71, 128.38, 127.61, 127.59, 125.46, 119.09,
(
Anhui Liangchen GF254) for column chromatography 114.87, 56.86.
1
was 200–300 mesh. H nuclear magnetic resonance (NMR)
and C NMR spectra were measured on a Bruker DRx500 3:1); m.p. 233.3–236.4°C; H NMR (500MHz, CDCl ):
(±)-4: White solid (2.68g, 73%); R =0.47 (PE/EtOAc,
f
1
3
1
3
1
13
NMR spectrometer ( H NMR: 500MHz, C NMR: δ=10.10 (s, 2H), 8.10–8.05 (m, 4H), 7.89 (d, J=1.9Hz,
25MHz). Low-resolution mass spectra were recorded on 2H), 7.68 (td, J=7.5, 1.5Hz, 2H), 7.61–7.50 (m, 6H), 7.33
an Agilent 5973N or a Waters GCT Premier spectrometer (dd, J=8.7, 1.8Hz, 2H), 7.27 (d, J=8.9Hz, 2H), 3.87 (s,
1
1
3
(
mass spectrometry electron ionization (MS EI)). High- 6H); C NMR (125MHz, CDCl ): δ=192.76, 155.65,
3
resolution mass spectra were obtained using a Bruker 146.07, 133.90, 133.54, 133.38, 132.76, 130.98, 129.96,
MicroTof II mass spectrometer (high-resolution mass spec- 129.76, 128.71, 128.38, 127.60, 127.60, 125.47, 119.10,
trometry electrospray ionization (HRMS ESI)). Melting 114.87, 56.87.
points were measured on an X-4 micrographic melting
point apparatus.
(
S)-/(R)-/(±)-2,2′-dimethoxy-[6,6′-
bis(2-methoxyethenyl)phenyl]-1,1′-
binaphthalene [(S)-5/(R)-5/(±)-5]
Starting materials
(
S)-/(R)-/(±)-6,6′-dibromo-[1,1′-binaphthalene]-2,2′-diol [(S)-/ A mixture of Ph P(CH OMe)·Cl (3.61g, 10.52mmol, 5.0
3 2
(
[
-
(
R)-/(±)-1], 6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthalene equiv.) and n-BuLi (674.14mg, 10.52mmol, 5.0 equiv.)
(S)-/(R)-/(±)-2], and 2,2′-(2,2′-dimethoxy-[1,1′-binaphthalene] was dissolved in anhydrous tetrahydrofuran (THF; 15mL)
6,6′-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) [(S)-/ at 0°C. After stirring at 0°C for 30min, a THF (10mL)
R)-/(±)-3] were prepared according to previous work (see solution of (S)-4/(R)-4/(±)-4 (1.10g, 2.10mmol, 1.0 equiv.)
15–17
Supplemental Material for details).
was added. The mixture was stirred at rt for 2h and then
quenched with water. After removing spare THF, the water
layer was extracted with EtOAc (3×20mL). The com-
bined extracts were washed with brine and dried over
Na SO . After removing the solvent, the crude residue was
(
S)-/(R)-/(±)-2,2′-(2,2′-dimethoxy-[1,1′-
binaphthalene]-6,6′-diyl)dibenzaldehyde
(S)-4/(R)-4/(±)-4]
2
4
[
purified by silica gel column chromatography (hexane/
A 250-mL three-neck bottom flask was charged with (S)-3/ EtOAc 15:1) to give a white solid.
(
R)-3/(±)-3 (4g, 7.06mmol, 1.0 equiv.), 2-bromobenzalde-
(S)-5: White solid (340mg, 28%); R =0.49 (PE/EtOAc,
f
1
hyde (2.9g, 15.52mmol, 2.2 equiv.), CsF (6.45g, 3:1); m.p. 89.3–92.5°C; H NMR (500MHz, CDCl ):
3
4
2.44mmol, 6.0 equiv.), and dioxane/H O (180mL, 2:1). δ=8.03 (d, J=9.0Hz, 2H), 7.89 (s, 2H), 7.52 (dd, J=9.0,
2
The flask was filled with argon and evacuated. This proce- 1.6Hz, 2H), 7.44 (d, J=7.4Hz, 2H), 7.37 (dt, J=7.4,
dure was repeated three times. Then Pd(dppf)Cl (258.5mg, 1.8Hz, 2H), 7.34–7.30 (m, 4H), 7.27–7.20 (m, 4H), 6.95
2
0
.35mmol, 0.05 equiv.) was added and the solution was (dd, J=12.9, 1.6Hz, 2H), 5.87 (d, J=12.8Hz, 2H), 3.85 (s,
1
3
heated under argon at 90°C for 8–10h. After cooling to 6H), 3.52 (s, 6H); C NMR (125MHz, CDCl ): δ=155.13,
3
room temperature (rt), the mixture was extracted with 148.91, 139.87, 136.53, 134.29, 132.89, 130.47, 129.63,
EtOAc (150mL). The organic layer was washed with brine 129.10, 128.68, 128.37, 127.38, 125.98, 125.04, 124.90,
(
3×50mL) and dried over anhydrous MgSO . After 119.39, 114.43, 104.68, 56.94, 56.54; MS (EI): m/z [M]+
4
removing the solvent, the crude residue was purified by calcd for C H O : 578.25; found: 578.
4
0
34
4
silica gel chromatography (hexane/EtOAc, 15:1) to furnish
the product as a white solid.
(R)-5: White solid (683mg, 56%); R =0.49 (PE/EtOAc,
f
1
3:1); H NMR (500MHz, CDCl ): δ=8.03 (d, J=9.0Hz,
3
(
S)-4: White solid (1.85g, 50%); R =0.47 (PE/EtOAc, 2H), 7.90 (s, 2H), 7.53 (d, J=9.0Hz, 2H), 7.44 (dd, J=7.6,
f
1
3
:1); m.p. 134.6–136.8°C; H NMR (500MHz, CDCl ): 1.5Hz, 2H), 7.37 (dd, J=7.3, 1.8Hz, 2H), 7.34–7.29 (m,
3
δ=10.10 (s, 2H), 8.09–8.06 (m, 4H), 7.89 (d, J=1.7Hz, 4H), 7.27–7.21 (m, 4H), 6.95 (d, J=12.9Hz, 2H), 5.87 (d,
1
3
2
H), 7.68 (td, J=7.5, 1.4Hz, 2H), 7.61–7.50 (m, 6H), 7.33 J=12.9Hz, 2H), 3.85 (s, 6H), 3.52 (s, 6H); C NMR
(
dd, J=8.7, 1.8Hz, 2H), 7.27 (d, J=9.1Hz, 2H), 3.87 (s, (125MHz, CDCl ): δ=155.13, 148.91, 139.87, 136.53,
3
1
3
6
1
1
H); C NMR (125MHz, CDCl ): δ=192.77, 155.64, 134.28, 132.89, 130.47, 129.63, 129.10, 128.68, 128.37,
3
46.07, 133.90, 133.54, 133.38, 132.76, 130.98, 129.96, 127.38, 125.98, 125.03, 124.90, 119.39, 114.43, 104.68,
29.76, 128.71, 128.38, 127.61, 127.59, 125.47, 119.10, 56.94, 56.54.

4
Journal of Chemical Research 00(0)
CsF (2.25g, 14.83mmol, 6.0 equiv.), and dioxane/H O
(
±)-5: White solid (426mg, 35%); R =0.49 (PE/EtOAc,
2
f
(120mL, 2:1). The flask was filled with argon and evacu-
3
:1); m.p. 118.2–121.4°C.
ated. This procedure was repeated three times. Then
Pd(dppf)Cl2 (90.45mg, 123.61μmol, 0.05 equiv.) was
added, and the solution was heated under argon at 90°C for
(
S)-/(R)-/(±)-2,2′-dimethoxy-1,1′-
bichrysene [(S)-6/(R)-6/(±)-6]
8
–10h. After cooling to rt, the mixture was extracted with
EtOAc. The organic layer was washed with brine
3×50mL) and dried over anhydrous MgSO . After
Trifluoromethane sulfonic acid (31μL, 0.35mmol, 0.6
equiv.) was added to a hexafluoroisopropanol (HFIP; 30mL)
solution of the crude mixture of (S)-5/(R)-5/(±)-5 (340mg,
.59mmol, 1.0 equiv.) at rt. After stirring at rt for 2h, the
reaction was quenched with saturated NaHCO aqueous
solution (pH 9) and then filtered and dried to give the crude
product of (S)-6/(R)-6/(±)-6 as a pink solid.
(
4
removing the solvent, the crude residue was purified by
silica gel chromatography (hexane/EtOAc, 10:1) to furnish
the product as a white solid.
18
0
3
(
S)-8: White solid (1.22g, 92%); R =0.7 (PE/EtOAc,
f
1
1
:1); m.p. 137.3–140.1°C; H NMR (500MHz, DMSO-d ):
6
δ=9.90 (s, 2H), 8.27 (d, J=8.7Hz, 4H), 7.74 (d, J=9.1Hz,
H), 7.69 (dd, J=5.4, 0.8Hz, 2H), 7.54–7.48 (m, 4H), 7.07
2
(
[
S)-/(R)-/(±)-[1,1′-bichrysene]-2,2′-diol
(S)-7/(R)-7/(±)-7]
13
(d, J=8.8Hz, 2H), 3.79 (s, 6H); C NMR (125MHz,
DMSO-d ): δ=185.99, 156.20, 155.74, 136.96, 133.74,
6
1
1
30.97, 130.19, 128.87, 128.34, 127.14, 126.94, 126.54,
25.70, 118.32, 115.55, 56.71; MS (EI): m/z [M] calcd for
The crude product of (S)-6/(R)-6/(±)-6 (0.59mmol, 1.0 equiv.)
+
was dissolved in CH Cl , and BBr (2.3mL, 23.6mmol, 40.0
2
2
3
C H O S : 534.10; found: 534.
equiv.) was slowly added at 0°C. The mixture was stirred at
°C for 1h and then at rt for 4h, poured into the water, and then
filtered and dried to give a brown solid.
32 22
4 2
(
R)-8: White solid (1.20g, 89%); R =0.7 (PE/EtOAc,
0
f
1
1
:1); m.p. 131.7–134.2°C; H NMR (500MHz, DMSO-d ):
6
δ=9.90 (s, 2H), 8.27 (d, J=9.5Hz, 4H), 7.74 (d, J=9.1Hz,
2H), 7.69 (d, J=5.3Hz, 2H), 7.56–7.48 (m, 4H), 7.07 (d,
J=8.8Hz, 2H), 3.79 (s, 6H); C NMR (125MHz,
DMSO-d ): δ=185.99, 156.20, 155.74, 136.96, 133.74,
(
S)-7: Brown solid (146mg, 51%); R =0.46 (PE/EtOAc,
f
1
1
:1); m.p.>300°C; H NMR (500MHz, DMSO-d6):
1
3
δ=9.56 (s, 2H), 8.93 (dd, J=28.0, 9.3Hz, 4H), 8.73 (d,
J=8.3Hz, 2H), 8.57 (d, J=9.6Hz, 2H), 8.09 (dd, J=18.8,
6
1
30.97, 130.19, 128.87, 128.34, 127.14, 126.94, 126.54,
8
.5Hz, 4H), 7.62 (ddd, J=35.6, 18.4, 8.3Hz, 6H), 7.27 (d,
1
3
125.70, 118.32, 115.55, 56.71.
J=9.4Hz, 2H); CNMR(125MHz, DMSO-d ):δ=154.57,
6
(
±)-8: White solid (0.92g, 70%); R =0.7 (PE/EtOAc,
1
33.49, 131.59, 130.58, 128.89, 128.84, 127.73, 127.24,
f
1
1
:1); m.p. 138.2–141.3°C; H NMR (500MHz, DMSO-d ):
1
26.45, 125.91, 125.10, 124.91, 124.53, 123.37, 121.96,
6
+
δ=9.90 (s, 2H), 8.27 (d, J=9.3Hz, 4H), 7.74 (d, J=9.2Hz,
H), 7.69 (d, J=5.3Hz, 2H), 7.55–7.47 (m, 4H), 7.07 (d,
118.63, 117.79, 99.98; MS (EI): m/z [M] calcd for
2
C H O : 486.16; found: 486.
3
6
22
2
1
3
J=8.8Hz, 2H), 3.79 (s, 6H); C NMR (125MHz,
DMSO-d ): δ=186.00, 156.19, 155.75, 136.94, 133.73,
1
1
(
R)-7: Brown solid (200mg, 70%); R =0.46 (PE/EtOAc,
f
1
1
:1); m.p.>300°C; H NMR (500MHz, DMSO-d ): δ=9.56
6
6
30.97, 130.18, 128.86, 128.32, 127.15, 126.93, 126.53,
25.69, 118.30, 115.55, 56.72.
(
(
s, 2H), 8.96 (d, J=9.2Hz, 2H), 8.90 (d, J=9.2Hz, 2H), 8.73
d, J=8.3Hz, 2H), 8.57 (d, J=9.4Hz, 2H), 8.11 (d, J=9.1Hz,
2
H), 8.07 (dd, J=7.8, 1.6Hz, 2H), 7.70–7.59 (m, 4H), 7.57
13
(d, J=9.1Hz, 2H), 7.26 (d, J=9.4Hz, 2H); C NMR
(
S)-/(R)-/(±)-2,2′-dimethoxy-[6,6′-
(
1
1
125MHz, DMSO-d ): δ=154.56, 133.49, 131.59, 130.58,
28.89, 128.85, 127.74, 127.24, 126.46, 125.90, 125.09,
6
bis(2-methoxyethenyl)thiophene]-1,1′-
binaphthalene [(S)-9/(R)-9/(±)-9]
24.92, 124.53, 123.37, 121.97, 121.93, 118.63, 117.79; MS
+
A mixture of Ph P(CH OMe)·Cl (1.64g, 4.78mmol, 5.0
(EI): m/z [M] calcd for C H O : 486.16; found: 486.
3
2
36
22
2
equiv.) and n-BuLi (306.43mg, 4.78mmol, 5.0 equiv.) was
dissolved in anhydrous THF (10mL) at 0°C. After stirring
at 0°C for 30min, a THF (5mL) solution of (S)-4/(R)-4/
(
±)-7: Brown solid (120mg, 42%); R =0.46 (PE/
f
1
EtOAc, 1:1); m.p.>300°C;
DMSO-d ): δ=9.56 (s, 2H), 8.96 (d, J=9.2Hz, 2H), 8.90
H
NMR (500MHz,
6
(±)-4 (500mg, 0.96mmol, 1.0 equiv.) was added. The mix-
(
d, J=9.2Hz, 2H), 8.72 (d, J=8.2Hz, 2H), 8.56 (d,
ture was stirred at rt for 2h and then quenched with water.
After removing THF, the water layer was extracted with
EtOAc (3×10mL). The combined extracts were washed
with brine and dried over Na SO . After removing the sol-
vent, the crude product was purified by silica gel column
chromatography (hexane/EtOAc 15:1) to give a white solid.
J=9.5Hz, 2H), 8.11 (d, J=9.2Hz, 2H), 8.07 (dd, J=7.9,
1
7
.6Hz, 2H), 7.69–7.60 (m, 4H), 7.57 (d, J=9.1Hz, 2H),
.26 (d, J=9.3Hz, 2H); C NMR (125MHz, DMSO-d6):
1
3
δ=154.57, 133.49, 131.58, 130.58, 128.89, 128.84, 127.72,
2
4
1
1
27.24, 126.45, 125.90, 125.10, 124.91, 124.53, 123.36,
21.95, 121.94, 118.63, 117.78; MS (EI): m/z [M] calcd
+
(
S)-9: White solid (246mg, 45%); R =0.46 (PE/EtOAc,
for C H O : 486.16; found: 486.
f
3
6
22
2
1
3
2
1
2
:1); H NMR (500MHz, CDCl ): δ=8.03 (d, J=9.0Hz,
3
H), 7.99 (s, 2H), 7.52 (d, J=9.0Hz, 2H), 7.41 (dd, J=8.8,
.9Hz, 2H), 7.25 (d, J=5.4Hz, 2H), 7.20 (d, J=8.7Hz,
H), 7.12 (d, J=5.3Hz, 2H), 7.05 (d, J=12.9Hz, 2H), 6.02
(
S)-/(R)-/(±)-2,2′-(2,2′-dimethoxy-[1,1′-
binaphthalene]-6,6′-diyl)bis(thiophene-3-
carbaldehyde) [(S)-8/(R)-8/(±)-8]
1
3
(d, J=13.0Hz, 2H), 3.84 (s, 6H), 3.62 (s, 6H); C NMR
A 250-mL three-neck round-bottom flask was charged with (125MHz, CDCl ): δ=155.30, 149.76, 136.33, 133.03,
3
(
3
S)-3/(R)-3/(±)-3 (1.40g, 2.47mmol, 1.0 equiv.), 2-bromo- 132.48, 129.76, 129.70, 129.16, 128.13, 127.96, 125.56,
-thiophenecarboxaldehyde (1.04g, 5.44mmol, 2.2 equiv.), 125.41, 124.33, 119.28, 114.59, 99.96, 56.90, 56.63.

An et al.
5
(
R)-9: White solid (305mg, 55%); R =0.46 (PE/EtOAc, Declaration of conflicting interests
f
3
:1); m.p. 138.9–144.3°C.
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
(
±)-9: White solid (430mg, 78%); R =0.46 (PE/EtOAc,
f
3
:1); m.p. 112.7–115.1°C.
Funding
(
S)-/(R)-/(±)-7,7′-dimethoxy-6,6′-
biphenanthro[1,2-b]thiophene [(S)-10/
R)-10/(±)-10]
The author(s) disclosed receipt of the following financial support
for the research, authorship, and/or publication of this article: This
study was supported by industrial funding from Jiangsu Visio
(
Trifluoromethane sulfonic acid (14.52μL, 0.16mmol, 0.6 Biotechnology Co., Ltd. China, which is acknowledged.
equiv.) was added to an HFIP (20mL) solution of the crude
mixture of (S)-9/(R)-9/(±)-9 (162mg, 0.27mmol, 1.0
equiv.) at rt. After stirring at rt for 2h, the reaction was
ORCID iD
Qiancai Liu
https://orcid.org/0000-0002-2270-1700
quenched with saturated NaHCO aqueous solution (pH 9)
3
and then filtered and dried to give the crude product of (S)-
Supplemental material
1
0/(R)-10/(±)-10 as a gray solid.
Supplemental material for this article is available online.
(
S)-/(R)-/(±)-[6,6′-biphenanthro[1,2-b]
References
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1
3
2
2
3
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3
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(
S)-11: Brown solid (121mg, 89%); R =0.4 (PE/EtOAc,
f
1
1
:1); m.p. 165.6–168.2°C; H NMR (500MHz, DMSO-d ):
6
1
δ=8.79 (d, J=9.1Hz, 2H), 8.75 (d, J=8.9Hz, 2H), 8.33 (s,
H), 8.07 (d, J=8.9Hz, 2H), 7.77 (d, J=5.3Hz, 2H), 7.69 (d,
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7
8
9
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1
3.
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377.
DMSO-d ): δ=154.49, 138.09, 137.46, 132.99, 127.61,
6
1
1
26.57, 125.73, 125.56, 125.07, 124.79, 124.54, 123.13,
2
calcd for C H NaO S : 521.0648; found: 521.0640.
32
18
2 2
(
R)-11: Brown solid (54mg, 40%); R =0.4 (PE/EtOAc, 12. de Bettencourt-Dias A, Viswanathan S and Rollett A. J Am
f
1
Chem Soc 2007; 129: 15436.
1
:1); m.p. 164.2–166.8°C; H NMR (500MHz, DMSO-d ):
6
1
3. Ebata H, Miyazaki E, Yamamoto T, et al. Org Lett 2007; 9:
δ=9.54 (s, 2H), 8.89 (d, J=9.5Hz, 2H), 8.80 (d, J=9.4Hz,
H), 8.12 (d, J=8.9Hz, 2H), 7.85–7.80 (m, 4H), 7.64 (d,
J=5.3Hz, 2H), 7.53 (d, J=9.1Hz, 2H), 7.18 (d, J=9.2Hz,
4
499.
4. Ogunlaja AS, Hosten E, Betz R, et al. RSC Adv 2016; 6:
9024.
2
1
3
13
2
1
1
H); C NMR (125MHz, DMSO): δ=154.48, 138.09,
1
1
5. Lv N, Xie M, Gu W, et al. Org Lett 2013; 15: 2382.
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37.46, 132.99, 127.60, 126.58, 125.73, 125.57, 125.07,
24.80, 124.54, 123.13, 122.93, 120.29, 118.60, 118.50; MS
6
64.
+
(
EI): m/z [M] calcd for C H O S : 498.07; found: 498.
32
18
2
2
17. Benmansour H, Shioya T, Sato Y, et al. Adv Funct Mater
(
±)-11: Brown solid (92mg, 68%); R =0.4 (PE/EtOAc,
2003; 13: 883.
f
+
1
:1); m.p. 164.6–167.2°C; MS (EI): m/z [M] calcd for 18. Fujita T, Takahashi I, Hayashi M, et al. Eur J Org Chem
C H O S : 498.07; found: 498.
2017; (2): 262.
3
2
18
2 2