Synthesis of bridged biarylbisquinones and effects of biaryl dihedral angles on photo- and electro-chemical properties

Article abstract of DOI:10.1016/j.tet.2016.02.001

A series of bridged biarylbisquinones, QBINOLs 1-4, and their corresponding monomers, QNaphs 5-6, were designed to demonstrate the influence of biaryl conformation on the photo- and electro-chemical properties of the molecules. All target compounds were synthesized from the Diels-Alder reaction between silyl enol ethers of the corresponding naphthyl or binaphthyl derivatives and p-benzoquinone. Addition of an OMe auxochrome or formation of the dimeric structures affect the absorption spectra and the energy band gap (Eg), but not the reduction potentials of the molecules. Narrowing the dihedral angles of the QBINOLs by shortening methylene bridges limited the contribution of bridging OR auxochromes and therefore resulted in lower HOMO levels and larger Eg.

Full text of DOI:10.1016/j.tet.2016.02.001

Tetrahedron 72 (2016) 1533e1540
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of bridged biarylbisquinones and effects of biaryl dihedral
angles on photo- and electro-chemical properties
Krittaphat Wongma, Nantiya Bunbamrung, Tienthong Thongpanchang *
Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road,
Bangkok 10400, Thailand
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 July 2015
Received in revised form 23 January 2016
Accepted 1 February 2016
Available online 2 February 2016
A series of bridged biarylbisquinones, QBINOLs 1e4, and their corresponding monomers, QNaphs 5e6,
were designed to demonstrate the influence of biaryl conformation on the photo- and electro-chemical
properties of the molecules. All target compounds were synthesized from the DielseAlder reaction
between silyl enol ethers of the corresponding naphthyl or binaphthyl derivatives and p-benzoquinone.
Addition of an OMe auxochrome or formation of the dimeric structures affect the absorption spectra and
the energy band gap (Eg), but not the reduction potentials of the molecules. Narrowing the dihedral
angles of the QBINOLs by shortening methylene bridges limited the contribution of bridging OR aux-
ochromes and therefore resulted in lower HOMO levels and larger Eg.
Keywords:
Auxochrome
Biarylbisquinone
Biaryl conformation
DielseAlder reaction
Energy band gap
Ó 2016 Elsevier Ltd. All rights reserved.
8
1. Introduction
in asymmetric reactions. In this work, a series of dimeric quinone-
conjugated biaryl structures (Fig. 1) were designed to investigate
The specific conformation of a biaryl axis greatly influences not
the effect of changing the conformation along the biaryl axis on the
only the molecular structure but also the electronic and optical
1
properties of biaryl molecules. Conformational studies of
binaphthyl derivatives are therefore of great interest. The ability to
control the biaryl conformation could lead to applications in the
2
design of asymmetric catalysts with improved enantioselectivity,
3
specific molecular recognition, and helical twisting of liquid
crystals. The conformation of biaryls, as described in terms of the
4
dihedral angle, can be controlled by varying the length of a linking
1
b,5
group between each aryl ring.
then possess a unique set of molecular properties due to the dif-
ference in the degree of -orbital overlap between the two
A specific conformation would
p
monomer subunits. Thus, by simply changing the length of the
bridge which is synthetically straightforward, the optical and
electrochemical properties of the materials can potentially be
manipulated.
Quinones with extended
p-conjugation attached with electron
donating and/or electron withdrawing functional groups have
widely been used in designing novel organic materials, e.g., helical
6
columnar liquid crystals and self-assembling helical aggregation,
7
nonlinear optical (NLO) materials, or as a chiral catalytic system
*
Corresponding author. Tel.: þ66 2 201 5130; fax: þ66 2 201 5139; e-mail ad-
Fig. 1. Chemical structures of QBINOLs 1e4, QNaph 5 and OMe-QNaph 6, as well as the
assigned dihedral angle (q).
dress: tienthong.tho@mahidol.ac.th (T. Thongpanchang).
http://dx.doi.org/10.1016/j.tet.2016.02.001
0
040-4020/Ó 2016 Elsevier Ltd. All rights reserved.

1534
K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
photo- and electronic properties of the system. The structure
consists of two parts, i.e., i) a biaryl with an alkyl linker which has
different chain lengths to control the molecular conformation of
the biaryl system, and ii) a quinone which is a key component used
for the study of photo- and electronic properties.
compound 18 in 87% yield.12 Compound 18 was then alkylated with
CH in the presence of K CO in refluxing acetone to provide
2
I
2
2
3
0
0
compound 19 in 64% yield. Bis-lithiation of 6,6 -dibromo-2,2 -
ꢀ
binaphthol 19 with n-BuLi at ꢁ78 C followed by trapping of the
dianion intermediate with N,N-dimethyl-acetamide yielded com-
13
pound 13 in 34% yield.
Subsequently, diacetyl binaphthols 13e16 were treated with
triisopropylsilyl triflate (TIPSOTf) in the presence of triethylamine
2
. Results and discussion
(
Et
3
N) to give silyl enol ethers 20e23, respectively. Without further
The synthesis of biarylbisquinone derivatives, assigned as QBI-
purification, the silyl enol ethers were then subjected to the Diel-
NOLs 1e4, as well as their corresponding monomeric quino-
neenaphthyl derivatives, QNaphs 5e6, is illustrated in Schemes 1
and 2. Oxidative coupling of commercially available 2-naphthol
7) was carried out by using FeCl in boiling H O to yield BINOL
3 2
8) in 91% yield.9 Then BINOL (8) was alkylated with CH
2 2
I ,
14
seAlder reaction with excess p-benzo-quinone in refluxing tol-
uene to afford the target QBINOLs 1e4 in low to moderate yields.
The high regioselectivity of the DielseAlder reaction was precedent
and could be rationalized in terms of the preservation of the
(
(
14c
naphthalene B ring’s aromaticity upon addition to the
a-position.
Br(CH
2
)
2
Br, Br(CH Br, and CH I to provide compounds 9e12 in 85,
2
)
3
3
5
c,d,10
The synthetic steps towards QNaph 5 and OMe-QNaph 6 are
2
1, 77, and 89% yield, respectively.
Scheme 1. Synthesis of QBINOLs 1e4. Conditions: (a) FeCl
0 (21%); (d) Br(CH Br, K CO , acetone, reflux, 6 h, 11 (77%); (e) CH
5 (97%), and 16 (95%); (g) CuCl
3
, boiling H
2
O, 3 h, 8 (91%); (b) CH
2 2 2 3 2 2 2 3
I , K CO , acetone, reflux, 2 days, 9 (85%); (c) Br(CH ) Br, K CO , acetone, reflux, 2 days,
ꢀ
1
1
2
)
3
2
3
3
I, K
2
CO , acetone, reflux, 3 h, (89%); (f) AcCl, AlCl
3
3
, 1,2-dichloroethane, N
, acetone, reflux, 2 days, (64%); (i) 1) n-BuLi, THF, N
2
, 0 C, 4 h, 13 (not observed), 14 (90%),
ꢀ
2
$2H
2
O, degassed MeOH, N
N, CH Cl , N
2
, rt, 12 h, (87%); (h) CH
2
I
2
, K
2
CO
3
2
, ꢁ78 C, 2 h, 2) N,N-dimethy-
ꢀ
ꢀ
lacetamide, ꢁ78 C, 4 h, (34%); (j) TIPSOTf, Et
3
2
2
2
, 0 C to rt, 4 h; (k) p-benzoquinone, toluene, reflux, 2 days, 1 (31%), 2 (13%), 3 (23%), and 4 (49%).
BINOLs 9e12 were then treated with acetyl chloride (AcCl) in
summarized in Scheme 2. FriedeleCrafts acetylation of naphtha-
the presence of a suspension of aluminium chloride (AlCl
3
) in 1,2-
lene (24) and 2-methoxynaphthalene (25) with AcCl in the pres-
ꢀ
ꢀ
dichloroethane under a N
2
atmosphere at 0 C for 4 h to achieve
ence of AlCl
3
in 1,2-dichloroethane at 0 C for 4 h gave 2-acetyl
11
the compounds 14e16 in 90, 97 and 95% yield, respectively.
naphthalene (26) in 19% yield and 6-methoxy-2-acetyl naphtha-
lene (28) in 51% yield, respectively, along with the undesired, more
However, under these conditions, compound 9 failed to give the
diacetylated product due to the cleavage of the acetal linker. Thus,
an alternative route towards compound 13 was needed. Oxidative
coupling reaction of a commercially available 6-bromo-2-naphthol
15
electronically favoured regioisomers, 1-acetyl naphthalene (27)
and 2-methoxy-1-acetyl naphthalene (29) in 73% and 46% yield,
respectively. Compounds 26 and 28 were then treated with TIPSOTf
(
17) with a stoichiometric amount of CuCl
2
$2H
2
O in degassed
3
in the presence of Et N to afford silyl enol ethers 30 and 31, which
MeOH under N atmosphere at room temperature for 12 h provided
2
were, without purification, then subjected to DielseAlder reaction

K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
1535
ꢀ
Scheme 2. Synthesis of QNaph 5 and OMe-QNaph 6. Conditions: (a) AcCl, AlCl
3
, 1,2-dichloroethane, N
2
, 0 C, 4 h, 26 (19%), 27 (73%), 28 (51%), and 29 (46%); (b) TIPSOTf, Et
3
N,
ꢀ
CH
2
Cl
2
, N
2
, 0 C to rt, 4 h; (c) p-benzoquinone, toluene, reflux, 2 days, 5 (8%), and 6 (67%).
with excess p-benzoquinone in refluxing toluene to provide the
desired adducts 5 and 6 in 8% and 67% yields, respectively, in two
steps.
Table 1
Photophysical properties of compounds 1e6
Compound
l
absa/nm (ε)
The absorption spectra of compounds 1e6 were measured in
ꢁ
5
CHCl
3
solution (1ꢂ10 M) as shown in Fig. 2 and the data were
C1-QBINOL 1
C2-QINOL 2
C3-QBINOL 3
257 (68,749), 337 (29,001), 351 (29,247), 442 (6710)
259 (69,322), 333 (25,286), 349 (25,641), 441 (6601)
summarized in Table 1. In Fig. 2, considering the absorption spectra
261 (67,820), 283 (53,587), 332 (26,871), 348 (23,838),
37 (5836)
of the quinone moiety in the region of 375e580 nm, assigned as n-
4
p
* transition,16 it was found that the band for OMe-QNaph 6 was
OMe-QBINOL 4
QNaph 5
264 (72,710), 291 (67,055), 336 (23,838), 351 (19,686),
461 (8103)
247 (56,456), 267 (46,621), 305 (27,745), 319 (29,630),
333 (32,908), 424 (6332)
bathochromically shifted to 442 nm, when compared with that of
QNaph 5 at 424 nm. The observed red shift is the expected outcome
17
from the addition of an auxochrome OMe group to QNaph. In
comparison between the monomeric OMe-QNaph 6 and the di-
meric OMe-QBINOL 4, both absorption spectra are similar in shape
but red shift was observed in the case of dimeric structure OMe-
OMe-QNaph 6
261 (86,341), 279 (66,317), 334 (16,872), 348 (20,642),
442 (7311)
a
Absorption wavelengths in dilute chloroform solution (1ꢂ10ꢁ5 M).
QBINOL 4. The shift implied the
p-electron contribution of two
phenanthryl units through the coplanar resonance structure in the
18
excited state as suggested by Friedel.
The absorption in the region of 240e360 nm represents the
19
characteristic patterns of the phenanthrene
pep* transition.
1
00000
C1-QBINOL 1
C2-QBINOL 1
C3-QBINOL 1
OMe-QBINOL 4
QNaph 5
Similar to the quinone region, the maximum absorption of the
OMe-QNaph 6, observed at 277 nm and 349 nm, was red shifted
when compared with the related absorptions of QNaph 5 at 268 nm
and 333 nm, indicating the effect of the electron donating OMe
group. The absorption peaks of the dimeric OMe-QBINOL 4 showed
a bathochromic shift at both 291 nm and 351 nm when compared
to the monomeric OMe-QNaph 6. Interestingly, changing the
lengths of the methylene linkages in QBINOLs 1e4 affected only the
90000
80000
70000
60000
50000
40000
30000
20000
10000
0
OMe-QNaph 6
absorptivity, but not their lmax. In the region of 265e295 nm, the
absorption intensity at around 290 nm decreased upon shortening
the linking bridge while the absorption at about 350 nm increased.
These experimental data support the effect of dihedral angle on the
electronic spectra of the binaphyl derivatives although it is in-
conclusive whether the effect of orbital overlap between the aux-
ochrome and
p-conjugate system or the extended conjugation
2
40260280300320340360380400420440460480500520540560580
Wavelength (nm)
between the two binaphthyls is a major contributor.
In order to evaluate the electrochemical properties of com-
pounds 1e6, cyclic voltammetry (CV) was studied in MeCN with
solution (1.0ꢂ10ꢁ M).
5
Fig. 2. UVevis absorption spectra of compounds 1e6 in CHCl
3
4 6
0.1 M of nBu NPF as supporting electrolyte. CV curves of all
Interestingly, when the dihedral angles
eC eC eC in Fig. 1) of the dimeric biaryl frameworks were
decreased from non-bridged OMe-QBINOL 4 to bridged QBINOLs
e3 by consecutively shortening the methylene linkage, the blue
shifts were observed. This observation is closely related to the
previous findings reported by Tebby et al. who studied the UV
absorption of biphenyl systems. The observed blue shift could be
explained in terms of the rigidity of the bridged binaphthyl struc-
tures which are locked by the linker. The linking groups constrain
the orientation of the oxygen lone pair electron orbitals leading to
the diminishing in the contribution of lone pair electrons of oxygen
(
q
,
defined as
compounds (Fig. 3), showed two reversible reduction peaks. Since
the two quinone moieties in all biarylbisquinones are further apart,
the first reduction peak corresponds to the one-electron reduction
of each quinone (Q), leading to the bis-semiquinone radical anion
C
2
1
1
0
0
2
1
ꢃ
ꢁ
(Q ). The second peak corresponds to the successive second one-
electron reduction, representing the formation of bis-quinone
5
a
2
ꢁ 20
dianion (Q ). The onset reduction potentials of compounds
1e6 were ꢁ1.13, ꢁ1.14, ꢁ1.13, ꢁ1.13, ꢁ1.13, and ꢁ1.14 V, respectively.
These values were almost identical suggesting that neither addition
of the OMe group, formation of dimeric structures nor the confor-
mation of the binaphthyls has a direct effect on the reduction
process.
atoms on the bridges to the p-system of the aromatic ring.

1536
K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
related to the reduction of the quinone moiety and were almost
C1-QBINOL 1
C2-QBINOL 2
C3-QBINOL 3
OMe-QBINOL 4
QNaph 5
identical. UV data showed a bathochromic shift as a result of the
addition of an electron donating auxochrome. Dimeric structures of
QBINOLs also affected the electronic properties through extended
conjugation especially in the aromatic region in the UV spectra.
However, when the dihedral angles of the dimeric QBINOLs were
decreased by shortening the bridges, the absorption edge in the
quinone region was slightly blue shifted. This observation suggests
that, despite a possible greater degree of extended conjugation
between the two aryl substructures, the degree of electronic con-
tribution from the OR group which was a key contributor to the
energy band gap, is limited due to the constrained orbital structure
of oxygen at the bridge, resulting in the lower HOMO level and the
larger Eg.
OMe-QNaph 6
25 μA
-
2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V vs Fc/Fc+)
4 6
Fig. 3. Cyclic voltammogram for compounds 1e6 in 0.1 M nBu NPF of MeCN solution.
Scan rate is 50 mV/s.
4
4
. Experimental section
.1. General method
g
The energy band gap (E ) between HOMO and LUMO of each
compound could then be calculated from the combination of the CV
and UV data (Fig. 4).21 The differences in the energy band gap was
mainly from the differences in HOMO levels since the LUMO levels,
as derived from the reduction potentials, are almost identical. Ac-
All materials, unless otherwise noted, were obtained from
commercial suppliers and used as provided. Solvents and reagents
were distilled before used. Tetrahydrofuran (THF) was freshly dis-
tilled from sodium/benzophenone under nitrogen to obtain dry and
oxygen free solvent. In addition, DMF, CH Cl , and N,N-dimethyla-
g
cordingly, E of OMe-QNaph 6 is smaller than that of QNaph 5 as
2
2
a result of the electron donating OMe group on the phenanthrene
cetamide (DMA) were distilled from CaH . Degassed MeOH was
2
2
2
ring which raises the EHOMO and consequently reduces the E
the biarylbisquinones, their E values are related with the dihedral
angle and the observed tendency of E is C1-1>C2-2>C3-3>OMe-4.
With respect to the effect of the electron donor on the E , the dif-
ference in E of QBINOLs 1e4 could thus be influenced by the di-
g
.
For
obtained by N gas bubbling under ultrasonication. Reactions were
2
g
typically monitored by thin layer chromatography (TLC) unless
g
otherwise noted. Melting points were determined by a Buchi M-
565 automated digital melting point apparatus and were reported
g
1
13
g
as observed. H and C spectra were recorded on Bruker Avance
DRX 300, 400 or 500 FT-NMR spectrometer. Mass spectra were
recorded on Bruker Data Analysis Esquire-LC spectrometer.
UVevisible absorption spectra were measured using Jasco V-530
UVevis spectrophotometer. The spectrograde chloroform was used
to dissolve test compounds for UVeVisible spectroscopy. CV ex-
periments were determined using Autolab PGSTAT12.
hedral angle which affects the electron donating ability of the
bridging OR auxochromes. The shorter the length of the bridge, the
smaller the dihedral angle of the binaphthyl core, and therefore the
EHOMO becomes lower in the order of C1-1<C2-2<C3-3<OMe-4.
This result then suggests that the orientation of lone pair electrons
of O atoms on the linking group is constrained with smaller di-
hedral angles, leading to a decrease in the electron-donating ability
of the O atom to the aromatic system, and consequently, ability to
raise HOMO levels.
0
0
9
4.2. 1,1 -Binaphthalene-2,2 -diol or BINOL (8)
To a suspension of 2-naphthol (7) (3.00 g, 20.81 mmol) in H
2
O
(
100 mL) was added anhydrous FeCl (5.00 g, 30.83 mmol) and the
3
decreasing band gap
mixture was then refluxed for 3 h. Subsequently, the crude product
was extracted from reaction mixture with ethyl acetate. The com-
bined organic layer was washed with water and brine, dried over
-
-
-
-
-
-
-
-
-
-
-
-
3.75
4.00
4.25
4.50
4.75
5.00
5.25
5.50
5.75
6.00
6.25
6.50
-
3.97
-3.96
-3.97
-3.97
-3.97
-3.96
LUMO
anhydrous Na
2 4
SO and evaporated to dryness. Finally, column
chromatography (Silica gel; 8:2 hexane/ethyl acetate as an eluent)
was followed to provide 1,1 -binaphthalene-2,2 -diol (8) (2.71 g,
0
0
ꢀ
ꢀ
9b
Band gap
HOMO
91%) as a white solid, mp 210e212 C (lit. mp 216e218 C);
max(neat) 3484, 3399, 1617, 1595, 1509, 1470, 1461, 1380, 1321,
v
ꢁ
1
1209, 1168, 1141, 1124, 825, 814, 750, 664 cm
;
d
H
(500 MHz,
CDCl
3
) 7.16 (2H, d, J 8.4 Hz, Ar), 7.30e7.33 (2H, m, Ar), 7.36e7.39
(4H, m, Ar), 7.89 (2H, d, J 8.1 Hz, Ar), 7.97 (2H, d, J 9.0 Hz, Ar);
d
C
-
6.17
-6.2
-6.25
-
6.22
3
-6.27
5
(125 MHz, CDCl ) 110.9, 117.8, 124.0, 124.2, 127.5, 128.4, 129.5, 131.4,
133.4, 152.7; HRMS (ESI): MNa , found: 309.0887. C20
quires 309.0886.
3
-
6.27
1
þ
4
6
14 2
H O Na re-
2
L
O
L
h
p
L
L
O
I
N
IN
h
p
O
O
B
a
N
IN
I
N
a
N
Q
B
B
Q
B
e
-
Q
e-Q
-
Q
-
Q
3
-
M
M
1
2
C
O
C
C
O
Compounds
Fig. 4. Energy diagram of compounds 1e6.
0
0
0
12
4
.3. 6,6 -Dibromo-[1,1 -binaphthalene]-2,2 -diol (18)
A
solution of 6-bromonaphthalen-2-ol (17) (10.00 g,
4
4.83 mmol) and CuCl $2H O (16.00 g, 93.85 mmol) in degassed
2
2
3
. Conclusion
In summary, QBINOLs 1e4, QNaph 5 and OMe-QNaph 6, were
methanol (150 mL) was stirred under nitrogen for 15 min. A solu-
tion of tert-butylamine (20.00 mL, 190.32 mmol) in methanol
(100 mL) was added over a period of 30 min. The resulting solution
was stirred at room temperature for 5 h. Then, the reaction mixture
was cooled down to 0 C and then 6 M of HCl was carefully added.
Methanol was evaporated under reduced pressure and the residue
successfully synthesized by using DielseAlder reaction between
silyl enol ether derivatives and p-benzoquinone as the key step. CV
data showed that the reduction potentials of all compounds were
ꢀ

K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
1537
þ
was diluted with ethyl acetate (100 mL) and washed with brine
2ꢂ50 mL). The organic layer was separated, dried over anhydrous
Na SO and evaporated under reduced pressure to yield a crude
126.3, 126.7, 127.6, 128.9, 129.4, 134.5, 157.6; HRMS (ESI): MNa ,
(
found 337.1204. C22
H
18
O
2
Na requires 337.1199.
2
4
0
0
product, which was then purified by column chromatography
4.4.5. 9,14-Dibromodinaphtho[2,1-d:1 ,2 -f][1,3]dioxepine
(19). White solid; mp 209e212 C (lit. mp 204e205 C); 64%
yield; vmax(neat) 2964, 2901, 2856, 1582, 1326, 1239, 1070, 1032,
0
10
ꢀ
ꢀ
27
(
Silica gel; 8:2 hexane/ethyl acetate as an eluent) to finally give 6,6 -
0
0
dibromo-[1,1 -binaphthalene]-2,2 -diol (18) (8.66 g, 87%) as a pale
ꢀ
ꢀ
23
ꢁ1
brown solid, mp 203e204 C (lit. mp 200e202 C);
v
max(neat)
976, 871, 809, 655, 559 cm
OCH
(2H, d, J 8.8 Hz, Ar), 7.82 (2H, d, J 8.8 Hz, Ar), 8.02 (2H, d, J 1.9 Hz, Ar);
H 3
; d (300 MHz, CDCl ) 5.61 (2H, s,
3
481, 1612, 1585, 1493, 1465, 1379, 1345, 1309, 1264, 1211, 1143,
2
O), 7.23 (2H, d, J 9.1 Hz, Ar), 7.31 (2H, dd, J 9.1 1.9 Hz, Ar), 7.42
ꢁ
1
1
067, 927, 875, 811, 735, 669 cm
J 9.0 Hz, Ar), 7.37 (2H, dd, J 8.9 2.0 Hz, Ar), 7.40 (2H, d, J 8.9 Hz, Ar),
.89 (2H, d, J 9.0 Hz, Ar), 8.05 (2H, d, J 2.0 Hz, Ar); (75 MHz, CDCl
10.7, 118.0, 119.0, 125.9, 130.5, 130.6, 130.7, 130.9, 131.9, 153.0;
H 3
; d (300 MHz, CDCl ) 6.96 (2H, d,
d
C
(75 MHz, CDCl
3
) 103.2, 119.2, 122.2, 125.9, 128.3, 129.6, 130.4,
130.5, 132.9, 151.6; HRMS (APCI): MH , found 454.9285.
þ
7
1
d
C
3
)
21 2 2
C H13Br O requires 454.9277.
þ
2 2
HRMS (ESI): MNa , found 464.9092. C20H12Br O Na requires
4
64.9096.
0
0
0
4
19
.4. General procedure A: synthesis of compounds 9e12 and
4.5. 1,1 -(Dinaphtho[2,1-d:1 ,2 -f][1,3]dioxepine-9,14-diyl) di-
13
ethanone (13)
0
0
To a mixture of BINOL (8) or dibromobinaphthol 18 (1.75 mmol)
and alkyldihalide (1.75 mmol) or methyliodide (17.5 mmol) in ac-
etone (50 mL) was added K CO (17.5 mmol). The reaction was then
To a solution of 9,14-dibromodinaphtho[2,1-d:1 ,2 -f][1,3]diox-
ꢀ
epine (19) (224 mg, 0.49 mmol) in dry THF (15 mL) at ꢁ78 C under
2
3
nitrogen, n-butyllithium (n-BuLi) (1.14 M solution in hexane,
refluxed until BINOL was completely consumed (monitored by
TLC). After that the reaction mixture was filtered by reduced
pressure, the filtrate was evaporated to dryness to yield the crude
product which was then purified by column chromatography (Silica
gel; 19:1 hexane/ethyl acetate as an eluent) to provide BINOL
derivatives.
1.08 mL, 1.23 mmol) was added dropwise. The mixture was kept
ꢀ
stirring at ꢁ78 C for an additional 2 h, then anhydrous N,N-
dimethylacetamide (0.18 mL, 1.94 mmol) was added dropwise. The
ꢀ
reaction mixture was stirred at ꢁ78 C for 2 h. The reaction mixture
4
was later quenched by saturated ammonium chloride (NH Cl)
aqueous solution and extracted with EtOAc (3ꢂ25 mL), dried over
anhydrous Na SO and the solvent was evaporated under reduced
2
4
0
0
10
4
1
.4.1. Dinaphtho[2,1-d:1 ,2 -f][1,3]dioxepine (9). White solid; mp
pressure. The crude product was chromatographed (Silica gel; 8:2
ꢀ
ꢀ
24
0
73e175 C (lit. mp 83e84 C); 85% yield; vmax(neat) 2958, 2920,
hexane/ethyl acetate as eluent) to provide 1,1 -(dinaphtho[2,1-
0
0
2
8
897, 2851, 1587, 1505, 1460, 1326, 1266, 1238, 1138, 1078, 969, 925,
d:1 ,2 -f][1,3]dioxepine-9,14-diyl)-diethanone (13) (64 mg, 34%) as
ꢁ1
ꢀ
16, 747, 662 cm
;
d
H
(300 MHz, CDCl
3
) 5.61 (2H, s, OCH
2
O), 7.22
a white solid, mp 160e163 C; vmax(neat) 3060, 2959, 2907, 1675,
(
2H, m, Ar), 7.34e7.45 (6H, m, Ar), 7.86 (2H, d, J 8.2 Hz, Ar), 7.90 (2H,
1617, 1586, 1464, 1358, 1242, 1187, 1073, 1032, 1001, 937, 823, 733,
ꢁ1
d, J 8.7 Hz, Ar);
1
3
d
C
(75 MHz, CDCl
3
) 103.1, 120.9, 125.0, 126.0, 126.1,
686 cm
OCH O), 7.47 (2H, d, J 8.9 Hz, Ar), 7.56 (2H, d, J 8.7 Hz, Ar), 7.85 (2H,
dd, J 8.9 and 1.6 Hz, Ar), 8.14 (2H, d, J 8.7 Hz, Ar), 8.58 (2H, d, J 1.6 Hz,
;
d
H
(400 MHz, CDCl
3
) 2.73 (6H, s, 2ꢂ MeC]O), 5.74 (2H, s,
þ
26.9, 128.4, 130.3, 131.8, 132.1, 151.2; HRMS (ESI): MNa , found:
2
21.0889. C21
14 2
H O Na requires 321.0886.
Ar);
d
C
(100 MHz, CDCl
3
) 26.7, 103.3, 122.0, 124.4, 125.8, 127.0, 130.6,
0
0
þ
4
(
.4.2. 4,5-Dihydrodinaphtho[2,1-e:1 ,2 -g][1,4]dioxocine
130.9, 132.3, 133.8, 134.3, 153.4, 197.7; HRMS (ESI): MNa , found
405.1098. C25H O Na requires 405.1097.
18 4
10
ꢀ
ꢀ
25
10). White solid; mp 219e222 C (lit. mp 214e215 C); 21%
yield; vmax(neat) 2959, 2926, 2855, 1587, 1504, 1465, 1326, 1277,
ꢁ1
1
222, 1200, 1076, 1051, 937, 886, 814, 754 cm
CDCl ) 4.16e4.27 (2H, m, OCH CH O), 4.38e4.49 (2H, m,
OCH CH O), 7.23e7.28 (4H, m, Ar), 7.40e7.45 (2H, m, Ar), 7.48
2H, d, J 8.8 Hz, Ar), 7.92 (2H, d, J 8.1 Hz, Ar), 8.01 (2H, d, J 8.8 Hz, Ar);
; d (300 MHz,
H
3
a
H
b
a b
H
a
H
b
a
H
b
4.6. General procedure B: synthesis of compounds 14, 15, 16,
26, and 28
(
d
C
(75 MHz, CDCl
31.0, 133.0, 156.5; HRMS (ESI): MNa , found 335.1041. C22
3
) 73.0, 122.4, 124.2, 124.7, 126.2, 127.1, 128.0, 130.7,
þ
1
H
16
O
2
Na
3
To a suspension of aluminium (III) chloride (AlCl ) (8.62 mmol)
requires 335.1043.
in 1,2-dichloroethane (20 mL), was added acetyl chloride (AcCl)
(
45 min. Dimeric BINOLs 14e16 (4.13 mmol) or naphthalene 24 and
ꢀ ꢀ
8.58 mmol) at 0 C. The reaction mixture was stirred at 0 C for
0
0
4
.4.3. 5,6-Dihydro-4H-dinaphtho[2,1-f:1 ,2 -h][1,5]dioxonine
10
ꢀ
ꢀ
25
(11). White solid; mp 266e268 C (lit. mp 165e166 C); 77%
2-methoxynapthalene 25 (8.27 mmol) was then added and stirred
ꢀ
yield; vmax(neat) 2968, 2945, 2874, 1587, 1504, 1467, 1327, 1269,
at 0 C for 4 h. Then, the reaction mixture was quenched with H
2
O
ꢁ
1
1
243, 1209, 1078, 1035, 1017, 818, 758, 700 cm
CDCl ) 1.97e2.00 (2H, m, OCH CH CH O), 4.32e4.45 (4H, m,
OCH CH CH O), 7.24e7.29 (4H, m, Ar), 7.38e7.42 (2H, m, Ar), 7.49
2H, d, J 8.9 Hz, Ar), 7.92 (2H, d, J 8.1 Hz, Ar), 7.99 (2H, d, J 8.9 Hz, Ar);
;
d
H
(300 MHz,
(30 mL), extracted with CH
phases were dried over anhydrous Na
evaporated to dryness. The crude product was purified by column
2
Cl
2
(3ꢂ50 mL). The combined organic
3
2
2
2
2
SO and the solvent was
4
2
2
2
(
chromatography with 2% CH
desired acetyl adducts.
2 2
Cl in hexane as eluent to obtain the
d
C
(75 MHz, CDCl
3
) 30.7, 71.9, 119.2, 123.9, 124.2, 126.2, 126.3, 128.1,
þ
129.6, 130.4, 133.4, 154.7; HRMS (ESI): MNa , found 349.1215.
0
0
0
C
H
23 18
O
2
Na requires 349.1199.
4.6.1. 1,1 -(4,5-Dihydrodinaphtho[2,1-e:1 ,2 -g][1,4] dioxo-cine-10,15-
11
ꢀ
diyl)diethanone (14). White solid; mp 219e221 C; 90% yield;
0
0
10
4
1
.4.4. 2,2 -Dimethoxy-1,1 -binaphthalene (12). White solid; mp
v
max(neat) 3058, 2953, 2926, 2865, 1673, 1615, 1588, 1468, 1439,
ꢀ
ꢀ
26
ꢁ1
96e198 C (lit. mp 224e225 C); 89% yield; vmax(neat) 2955,
1356, 1258, 1225, 1185, 1070, 937, 895, 821, 734, 697 cm
(300 MHz, CDCl
OCH CH O), 4.42e4.52 (2H, m, OCH
8.9 Hz, Ar), 7.53 (2H, d, J 8.8 Hz, Ar), 7.79 (2H, dd, J 8.9 1.6 Hz, Ar),
8.14 (2H, d, J 8.8 Hz, Ar), 8.55 (2H, d, J 1.6 Hz, Ar); (75 MHz, CDCl
26.6, 72.7, 123.5, 123.8, 124.5, 127.1, 130.0, 130.2, 132.6, 133.5, 135.1,
; d
H
2
918, 2837, 1618, 1589, 1504, 1460, 1263, 1248, 1147, 1089, 1062,
3
) 2.70 (6H, s, 2ꢂ MeC]O), 4.16e4.26 (2H, m,
ꢁ
1
1049, 1018, 895, 809, 745, 678 cm
;
d
H
(300 MHz, CDCl
3
) 3.80 (6H,
a
H
b
a
H
b
a
H
b
CH O), 7.25 (2H, d, J
a b
H
s, 2ꢂ MeO), 7.14 (2H, d, J 8.5 Hz, Ar), 7.22e7.27 (2H, m, Ar), 7.32e7.37
(
(
2H, m, Ar), 7.49 (2H, d, J 9.0 Hz, Ar), 7.90 (2H, d, J 8.2 Hz, Ar), 8.01
2H, d, J 9.0 Hz, Ar); (75 MHz, CDCl ) 55.2, 105.7, 118.7, 123.6,
d
C
3
)
d
C
3

1538
K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
þ
ꢀ
1
58.5, 197.7; HRMS (ESI): MNa , found 419.1248. C26
H
20
O
4
Na re-
(1.0 mL for diacetyl binaphthyl derivatives) was added at 0 C under
nitrogen. The reaction mixture was stirred for 10 min, followed by
addition of triisopropylsilyl triflate (TIPSOTf) (1.24 mmol for acetyl
naphthalene derivatives) or (2.48 mmol for diacetyl binaphthyl
derivatives). The reaction mixture was warmed up to room tem-
perature and stirred for 4 h. Then, the reaction mixture was
quenched with 10% NaOH. The reaction mixture was then washed
quires 419.1254.
0
0
0
4
1
.6.2. 1,1 -(5,6-Dihydro-4H-dinaphtho[2,1-f:1 ,2 -h][1,5] diox-onine-
1,16-diyl) diethanone (15). White solid; mp 295e298 C; 97%
yield; vmax(neat) 3060, 2948, 2887, 1676, 1616, 1473, 1424, 1358,
271, 1218, 1189, 1072, 1033, 951, 897, 819, 736, 700 cm
300 MHz, CDCl ) 1.99e2.05 (2H, m, OCH CH CH
O), 2.72 (6H, s, 2ꢂ
MeC]O), 4.36e4.51 (4H, m, OCH CH CH O), 7.28 (2H, d, J 8.9 Hz,
Ar), 7.56 (2H, d, J 8.9 Hz, Ar), 7.82 (2H, dd, J 8.9 1.6 Hz, Ar), 8.13 (2H,
d, J 8.9 Hz, Ar), 8.56 (2H, d, J 1.6 Hz, Ar); (75 MHz, CDCl ) 26.6,
0.5, 72.0, 120.0, 123.5, 124.7, 126.2, 129.4, 130.5, 131.7, 133.1, 135.6,
11
ꢀ
ꢁ
1
1
(
; d
H
3
2
2
2
with saturated NaHCO (3ꢂ20 mL). The organic phase was dried
3
2
2
2
over anhydrous Na SO . The solvent was removed under reduced
2
4
pressure and dried under vacuum to afford the desired silyl enol
ether. The product would be used in the next step without further
purification.
d
C
3
3
1
þ
57.1, 197.9; HRMS (ESI): MH , found 411.1583. C27
H
23
O
4
requires
0 0
4.7.1. 9,14-Bis(1-((triisopropylsilyl)oxy)vinyl)dinaphtho[2,1-d:1 ,2 -f]
411.1591.
[
1,3]dioxepine (20). Brown oil; vmax(neat) 2940, 2864, 1679, 1613,
0
0
1
0
0
ꢁ1
4
.6.3. 1,1 -(2,2 -Dimethoxy-[1,1 -binaphthalene]-6,6 -diyl) di-
1583, 1463, 1295, 1190, 1079, 1006, 882, 809, 674 cm
(400 MHz, CDCl CH)
) 1.17 (36H, d, J 7.2 Hz, 2ꢂ (Me
(6H, sep, J 7.2 Hz, 2ꢂ (Me CH) SiO), 4.53 (2H, d, J 1.6 Hz, 2CH
4.99 (2H, d, J 1.6 Hz, 2CH ]), 5.70 (2H, s, OCH O), 7.46e7.48 (4H,
m, Ar), 7.58 (2H, dd, J 9.0 1.6 Hz, Ar), 7.99 (2H, d, J 8.7 Hz, Ar), 8.24
(2H, d, J 1.6 Hz, Ar); (100 MHz, CDCl ) 12.8, 18.1, 90.7, 103.1, 121.1,
; d
H
1
ꢀ
C
ethanone (16). Yellow solid; mp 250e252
(lit. mp
3
2
3
SiO), 1.31e1.37
]),
ꢀ
11
1
1
(
7
9
1
84e186 C); 95% yield; vmax(KBr) 3007, 2946, 2842, 1669, 1620,
2
3
a b
H
ꢁ1
588, 1355, 1247, 1174, 834, 796 cm
6H, s, 2ꢂ MeC]O), 3.83 (6H, s, 2ꢂ MeOAr), 7.13 (2H, d, J 8.9 Hz, Ar),
.55 (2H, d, J 9.1 Hz, Ar), 7.80 (2H, dd, J 8.9 1.6 Hz, Ar), 8.15 (2H, d, J
.1 Hz, Ar), 8.54 (2H, d, J 1.6 Hz, Ar); (75 MHz, CDCl ) 26.5, 56.5,
14.3,118.7,124.6, 125.3,127.9, 130.6,131.6, 132.5,136.2,157.0,197.8;
;
d
H
(300 MHz, CDCl
3
) 2.71
a
H
b
2
d
C
3
d
C
3
123.8, 124.7, 126.0, 126.6, 130.9, 131.5, 131.9, 134.3, 151.4, 155.7;
HRMS (ESI) MH , found 695.3941. C43
þ
59
H O
4
Si
2
requires 695.3946.
þ
23 4
HRMS (APCI): MH , found 399.1596. C26H O requires 399.1591.
4
.7.2. 10,15-Bis(1-((triisopropylsilyl)oxy)vinyl)-4,5-dihydrodi-naph-
0
0
4
.6.4. 1-(Naphthalen-2-yl)ethanone (26).11 Pale yellow liquid; 19%
yield; vmax(neat) 3058, 3004, 2923, 2853, 1675, 1627, 1465, 1430,
tho[2,1-e:1 ,2 -g][1,4]dioxocine (21). Brown oil; vmax(neat) 2940,
2864, 1611, 1586, 1465, 1332, 1294, 1191, 1076, 1011, 881, 805,
ꢁ1
ꢁ1
1362, 1275, 1226, 1191, 1129, 944, 861, 819, 747 cm
;
d
H
(300 MHz,
673 cm
(Me
4.12e4.18 (2H, m, OCH
CH O), 4.46 (2H, d, J 1.6 Hz, 2CH
2CH ]), 7.17 (2H, d, J 9.0 Hz, Ar), 7.40 (2H, d, J 8.8 Hz, Ar), 7.47
(2H, dd, J 9.0 1.6 Hz, Ar), 7.95 (2H, d, J 8.8 Hz, Ar), 8.17 (2H, d, J 1.6 Hz,
Ar); (100 MHz, CDCl ) 12.9, 17.9, 73.2, 109.3, 120.4, 120.7, 124.5,
125.2, 126.5, 128.7, 129.4, 132.2, 133.3, 134.6, 134.8, 135.5, 140.7,
157.3, 158.4, 185.4, 187.0; HRMS (ESI): MH , found 709.4108.
C
;
d
H
(400 MHz, CDCl
3
) 1.13 (36H, d, J 7.0 Hz, 2ꢂ
CH) SiO),
O), 4.34e4.41 (2H, m, OCH
]), 4.91 (2H, d, J 1.6 Hz,
CDCl
3
) 2.73 (3H, s, MeC]O), 7.52e7.63 (2H, m, Ar), 7.86e7.90 (2H,
2
CH)
3
SiO), 1.27e1.35 (6H, sep, J 7.0 Hz, 2ꢂ Me
2
3
m, Ar), 7.96 (1H, d, J 8.4 Hz, Ar), 8.03 (1H, dd, J 8.6 1.7 Hz, Ar), 8.50
a
b
H CH
a
H
b
a b-
H
(
1H, s, Ar);
d
C
(75 MHz, CDCl
3
) 26.7, 123.9, 126.7, 127.7, 128.4, 129.5,
a
H
b
a b
H
þ
130.2, 132.5, 134.4, 135.5, 198.1; HRMS (ESI): MH , found 171.0803.
a b
H
C
12
H11O requires 171.0804.
d
C
3
4
.6.5. 1-(Naphthalen-1-yl)ethanone (27).11 Pale yellow liquid; 73%
þ
yield; vmax(neat) 3050, 3004, 2923, 2852, 1673, 1572, 1506, 1429,
ꢁ
1
1
2
8
352, 1276, 1237, 1189, 1126, 1014, 940 cm
;
d
H
(300 MHz, CDCl
.73 (3H, s, MeC]O), 7.45e7.64 (3H, m, Ar), 7.85e7.99 (3H, m, Ar),
.78 (1H, d, J 8.4 Hz, Ar); (75 MHz, CDCl ) 29.8,124.2,125.9,126.3,
27.9, 128.3, 128.6, 130.0, 132.9, 133.8, 135.2, 201.7; HRMS (ESI)
3
)
44
61
H O
4
2
Si requires 709.4103.
d
C
3
4.7.3. 11,16-Bis(1-((triisopropylsilyl)oxy)vinyl)-5,6-dihydro-4H-di-
naphtho[2,1-f:1 ,2 -h][1,5]dioxonine (22). Brown oil;
2938, 2864,1613,1587, 1464,1381,1296,1251, 1078,1043, 1010, 882,
0
0
1
vmax(neat)
þ
MNa , found 193.0626. C12
H10ONa requires 193.0624.
ꢁ
1
8
02, 672 cm
(Me CH)
SiO), 1.26e1.36 (6H, sep, J 7.2 Hz, 2ꢂ Me
1.93e1.95 (2H, m, OCH CH CH O), 4.31e4.39 (4H, m, OCH
CH O), 4.44 (2H, d, J 1.4 Hz, 2CH ]), 4.90 (2H, d, J 1.4 Hz,
2CH ]), 7.18 (2H, d, J 8.9 Hz, Ar), 7.42 (2H, d, J 8.8 Hz, Ar), 7.49
(2H, dd, J 8.9 1.6 Hz, Ar), 7.93 (2H, d, J 8.8 Hz, Ar), 8.16 (2H, d, J 1.6 Hz,
Ar); (100 MHz, CDCl ) 12.8, 18.1, 30.6, 71.9, 90.0, 119.3, 123.7,
;
d
H
(400 MHz, CDCl
3
) 1.13 (36H, d, J 7.2 Hz, 2ꢂ
CH) SiO),
CH
11
4
.6.6. 1-(6-Methoxynaphthalen-2-yl)ethanone (28). White solid;
2
3
2
3
ꢀ
ꢀ
28
mp 99e101 C (lit. mp 98e100 C); 51% yield; vmax(KBr) 3063,
2
2
2
2
2-
ꢁ1
3
002, 2966, 2935,1675,1602,1479,1440,1359,1275, 821, 742 cm
(300 MHz, CDCl ) 2.72 (3H, s, MeC]O), 3.97 (3H, s, MeOAr), 7.17
1H, d, J 2.4 Hz, Ar), 7.22 (1H, dd, J 8.9 2.4 Hz, Ar), 7.78 (1H, d, J
;
2
a b
H
d
H
3
a b
H
(
8
8
.6 Hz, Ar), 7.87 (1H, d, J 8.9 Hz, Ar), 8.03 (1H, dd, J 8.6 1.7 Hz, Ar),
.41 (1H, d, J 1.7 Hz, Ar); (75 MHz, CDCl ) 26.5, 55.4, 105.7, 119.7,
24.6, 127.1, 127.8, 130.0, 131.1, 132.6, 137.2, 159.7, 197.8; HRMS
d
C
3
d
C
3
124.0, 124.5, 125.9, 130.1, 130.2, 133.2, 133.6, 154.9, 156.0; HRMS
(ESI): MH , found 723.4255. C45
þ
1
(
63
H O
4
Si
2
requires 723.4259.
þ
13 2
APCI): MH , found 201.0942. C13H O requires 201.0910.
0
0
0
4.7.4. 6,6 -Bis[1-(triisopropylsiloxy)-ethenyl]-2,2 -dimethoxy-1,1 -bi-
11
4
.6.7. 1-(2-Methoxynaphthalen-1-yl)ethanone (29). White solid;
naphthalene) (23). Pale brown solid; vmax(KBr) 3071, 2944, 2866,
ꢀ
ꢀ
29
ꢁ1
mp 53e55 C (lit. mp 59 C); 46% yield;
3H, s, MeC]O), 3.81 (3H, s, MeOAr), 7.12 (1H, d, J 9.1 Hz, Ar),
.17e7.26 (1H, m, Ar), 7.30e7.37 (1H, m, Ar), 7.61e7.67 (2H, m, Ar),
.72 (1H, d, J 9.1 Hz, Ar); (75 MHz, CDCl 32.6, 56.2, 112.7, 123.5,
23.9, 124.9, 127.5, 128.0, 128.7, 130.2, 131.4, 153.9, 205.0; HRMS
d
H
(300 MHz, CDCl
3
) 2.53
1638, 1624, 1585, 1460, 1384, 1269, 1176, 1146, 808, 737 cm
(300 MHz, CDCl CH)
) 1.19 (36H, d, J 7.0 Hz, 2ꢂ (Me
(6H, sep, J 7.0 Hz, 2ꢂ Me CH) SiO), 3.79 (6H, s, 2ꢂ MeOAr), 4.47 (2H,
d, J 1.8 Hz, 2CH ]), 4.92 (2H, d, J 1.8 Hz, 2CH ]), 7.08 (2H, d, J
9.0 Hz, Ar), 7.47 (2H, d, J 9.0 Hz, Ar), 7.51 (2 h, dd, J 9.0 1.8 Hz, Ar),
8.00 (2H, d, J 9.0 Hz, Ar), 8.20 (2H, d, J 1.8 Hz, Ar); (75 MHz, CDCl
2.8, 18.1, 56.8, 89.7, 114.3, 119.4, 124.0, 124.4, 125.0, 128.8, 130.0,
; d
H
(
7
7
1
3
2
3
SiO), 1.32e1.39
2
3
d
C
3
)
d
a
H
b
a b
H
þ
(
ESI): MNa , found 223.0735. C13
H13NaO
2
requires 223.0730.
d
C
3
)
1
þ
4
3
.7. General procedure C: synthesis of silyl enol ethers 20e23,
0, and 31
132.9, 133.8, 155.3, 156.1; HRMS (ESI): MH , found 711.4261.
Si requires 711.4259.
C
44
H
63
O
4
2
To a solution of acetyl naphthalene derivatives or diacetyl
4.7.5. Triisopropyl((1-(naphthalen-2-yl)vinyl)oxy)silane (30). Pale
brown solid; vmax(neat) 2942, 2893, 2866, 2726, 1612, 1505, 1464,
binaphthyl derivatives (0.20 g, 1.18 mmol) in dry CH
2 2
Cl (5 mL),
ꢁ
1
triethylamine (Et N) (0.5 mL for acetyl naphthalene derivatives) or
3
1309, 1250, 1015, 882, 804, 677 cm
; d (400 MHz, CDCl ) 1.06
H 3

K. Wongma et al. / Tetrahedron 72 (2016) 1533e1540
1539
(
(
CH
1
1
C
18H, d, J 7.4 Hz, (Me
Me CH) SiO), 4.43 (1H, d, J 1.8 Hz, CH
]), 7.32e7.36 (2H, m, Ar), 7.64e7.75 (4H, m, Ar), 8.05 (1H, s,
2
CH)
3
SiO), 1.18e1.25 (3H, sep, J 7.4 Hz,
(6H, m, 2ꢂ Me
4.35e4.40 (2H, m, OCH
OCH CH CH O), 6.94 (2H, d, J 10.1 Hz, 2CH
J 10.1 Hz, 2CH ]CH ), 7.39 (2H, d, J 9.2 Hz, Ar), 7.52 (2H, s, Ar), 7.58
(2H, d, J 9.3 Hz, Ar), 8.02 (2H, d, J 9.3 Hz, Ar), 8.47 (2H, d, J 9.2 Hz, Ar);
(100 MHz, CDCl ) 12.9, 18.0, 30.1, 71.7, 109.1, 116.4, 120.7, 124.1,
25.0, 125.6, 128.1, 129.3, 132.2, 132.5, 134.7, 134.8, 135.5, 140.8,
2
CH)
3
SiO), 1.99e2.01 (2H, m, OCH
CH CH O), 4.44e4.49 (2H, m,
]CH ), 7.09 (2H, d,
2 2 2
CH CH O),
2
H
3
a
H
b
]), 4.90 (1H, d, J 1.8 Hz,
a
H
b
2
a b
H
a
b
a
H
b
2
a
H
b
a
b
H);
d
C
(100 MHz, CDCl
3
) 12.8, 18.1, 90.8, 123.5, 124.3, 126.0, 127.5,
a
b
þ
28.5, 133.2, 135.1, 156.0; HRMS (ESI): MH , found 349.1955.
21
H30NaOSi requires 349.1958.
d
C
3
1
þ
4
.7.6. Triisopropyl((1-(6-methoxynaphthalen-2-yl)vinyl)oxy) silane
156.8, 157.3, 185.5, 187.0; HRMS (ESI): MH , found 931.4058.
(
1
7
3
31). Brown oil; vmax(neat) 3062, 2944, 2866, 1632, 1598, 1463,
C
57
H
63
O
8
Si
2
requires 931.4056.
ꢁ1
388, 1260, 1164, 804, 737 cm
CH) SiO), 1.16e1.29 (3H, sep, J 7.0 Hz, (Me
.78 (3H, s, MeOAr), 4.38 (1H, d, J 1.8 Hz, CH ]), 4.85 (1H, d, J
]), 6.98e7.04 (2H, m, Ar), 7.53e7.64 (3H, m, Ar), 7.97
(75 MHz, CDCl ) 12.8, 18.1, 55.2, 89.9, 105.6, 118.8,
24.0, 124.2, 126.4, 128.6, 130.0, 133.1, 134.4, 156.1, 157.9; HRMS
;
d
H
(300 MHz, CDCl
3
) 1.06 (18H, d, J
0
0
0
.0 Hz, (Me
2
3
2
CH) SiO),
3
4.8.4. 3,3 -Dimethoxy-7,7 -bis((triisopropylsilyl)oxy)[4,4 -bibenzo[c]
phenanthrene]-9,9 ,12,12 -tetraone or OMe-QBINOL 4. Red solid; mp
282e284 C; 49% yield; vmax(KBr) 2945, 2867, 1667, 1613, 1573,
1463, 1386, 1244, 1169, 828, 737 cm
(36H, d, J 7.5 Hz, 2ꢂ (Me CH) SiO), 1.41e1.51 (6H, sep, J 7.5 Hz, 2ꢂ
Me CH)
SiO), 3.86 (6H, s, 2ꢂ MeOAr), 6.96 (2H, d, J 10.1 Hz, 2CH
CH ), 7.12 (2H, d, J 10.1 Hz, 2CH ]CH ), 7.32e7.39 (4H, m, Ar), 7.53
(2H, s, Ar), 7.99 (2H, d, J 9.4 Hz, Ar), 8.54 (2H, d, J 9.4 Hz, Ar);
(75 MHz, CDCl ) 13.0, 18.0, 56.3, 108.9, 110.8, 119.4, 120.4, 123.7,
0
0
a
H
b
ꢀ
1
.8 Hz, CH
a
H
b
ꢁ
1
(
1H, s, Ar);
d
C
3
H 3
; d (300 MHz, CDCl ) 1.15
1
2
3
þ
(
ESI): MH , found 379.2066. C22
H32NaO
2
Si requires 379.2064.
2
3
a
]
b
a
b
4
.8. General procedure D: synthesis of QBINOLs 1e4 and
d
C
QNaphs 5L6
3
1
25.0, 127.7, 128.9, 132.1, 132.8, 134.7, 135.1, 135.4, 140.9, 157.1, 157.3,
þ
A solution of silyl enol ethers (0.83 mmol) and p-benzoquinone
185.6, 187.1; HRMS (APCI): MH , found 919.4043. C56
H
63
O
8
Si
2
re-
(
9.92 mmol for naphthyl silyl enol ethers) or (19.84 mmol for
quires 919.4056.
binaphthyl silyl enol ethers) in toluene (20 mL) was refluxed for
8 h. The reaction mixture was then cooled down to room tem-
4
4.8.5. 6-((Triisopropylsilyl)oxy)benzo[c]phenanthrene-1,4-dione or
QNaph 5. Red solid; 8% yield; vmax(neat) 2947, 2867, 1663, 1613,
1567, 1526, 1383, 1301, 1253, 1217, 1088, 1064, 881, 848, 781, 753,
perature. The remaining p-benzoquinone was filtered and washed
with hexane. The solution was collected and the solvent was
evaporated to dryness. The crude product was purified by column
chromatography (Silica gel; 8:2 hexane/ethyl acetate as an eluent)
to provide quinone-naphthyl derivatives or quinone-binaphthyl
derivatives.
ꢁ1
686 cm
SiO), 1.49e1.53 (3H, sep, J 7.5 Hz, (Me
10.1 Hz, CH ]CH ), 7.06 (1H, d, J 10.1 Hz, CH
(1H, m, Ar), 7.56 (1H, s, Ar), 7.59e7.62 (1H, m, Ar), 7.87e7.89 (2H,
m, Ar), 8.20 (1H, d, J 9.0 Hz, Ar), 8.34 (1H, d, J 8.4 Hz, Ar);
(100 MHz, CDCl ) 13.0, 18.0, 109.4, 119.7, 124.9, 125.6, 127.9, 128.1,
;
d
H
(400 MHz, CDCl
3
) 1.19 (18H, d, J 7.5 Hz, (Me
CH) SiO), 6.92 (1H, d, J
]CH ), 7.44e7.48
2 3-
CH)
2
3
a
b
a
b
d
C
4.8.1. 11,16-Bis((triisopropylsilyl)oxy)benzo[5,6]phenanthro [2,1-d]
3
benzo[5,6]phenanthro[1,2-f][1,3]dioxepine-6,9,18,21-tetraone or C1-
QBINOL 1. Red solid; mp 290e294 C; 31% yield; vmax(neat) 2944,
128.4, 129.2, 130.1, 130.2, 132.0, 134.0, 134.5, 135.4, 140.7, 157.2,
ꢀ
þ
185.4, 186.9; HRMS (ESI): MH , found 431.2032. C27
quires 431.2037.
31 3
H O Si re-
2
865, 1660, 1611, 1574, 1509, 1416, 1383, 1341, 1295, 1244, 1062,
ꢁ1
1
(
(
1
(
006, 926, 883, 833, 798, 731 cm
36H, m, 2ꢂ (Me CH) SiO), 1.41e1.48 (6H, m, 2ꢂ Me
2H, s, OCH O), 6.97 (2H, d, J 10.2 Hz, 2CH ]CH
0.2 Hz, 2CH ]CH ), 7.45 (2H, d, J 9.1 Hz, Ar), 7.58 (2H, s, Ar), 7.78
2H, d, J 9.3 Hz, Ar), 8.04 (2H, d, J 9.3 Hz, Ar), 8.48 (2H, d, J 9.1 Hz, Ar);
(100 MHz, CDCl ) 12.9,17.9, 103.5,109.6,119.3,120.6,125.2,126.2,
27.6, 128.4, 129.4, 132.4, 133.1, 134.0, 134.8, 135.6, 140.7, 152.9,
;
d
H
(400 MHz, CDCl
3
) 1.11e1.14
2
3
2
CH)
3
SiO), 5.74
4.8.6. 10-Methoxy-6-((triisopropylsilyl)oxy)benzo[c]phenan-threne-
1,4-dione or OMe-Qnaph 6. Red viscous liquid; 67% yield; vmax(KBr)
3061, 2944, 2866, 1666, 1618, 1573, 1462, 1384, 1246, 1162, 825,
2
a
b
), 7.11 (2H, d, J
a
b
ꢁ
1
737 cm
1.48e1.56 (3H, sep, J 7.4 Hz, (Me
(1H, d, J 10.1 Hz, CH ]CH ), 7.05 (1H, d, J 10.1 Hz, CH
;
d
H
(300 MHz, CDCl
3
) 1.22 (18H, d, J 7.4 Hz, (Me
CH) SiO), 3.98 (3H, s, MeOAr), 6.91
]CH ), 7.11
2 3
CH) SiO),
d
C
3
2
3
1
a
b
a
b
þ
157.3, 185.4, 186.9; HRMS (ESI): MNa , found 925.3564.
(1H, dd, J 9.3, 2.7 Hz, Ar), 7.21 (1H, d, J 2.7 Hz, Ar), 7.53 (1H, s, Ar),
7.80 (1H, d, J 8.9 Hz, Ar), 8.20 (1H, d, J 8.9 Hz, Ar), 8.27 (1H, d, J
C
H
55 58
O
8
2
Si Na requires 925.3562.
C 3
9.3 Hz, Ar); d (75 MHz, CDCl ) 13.0, 18.0, 55.4, 107.5, 108.7, 115.6,
4
.8.2. 12,17-Bis((triisopropylsilyl)oxy)-2,3-dihydrobenzo
[5,6]phe-
120.3, 123.5, 124.8, 128.9, 129.5, 131.8, 132.1, 134.6, 135.3, 135.8,
140.7, 157.2, 159.2,185.5,186.8; HRMS (APCI): MH , found 461.2145.
þ
nanthro[2,1-e]benzo[5,6]phenanthro[1,2-g][1,4]dioxo-cine-
7,10,19,22-tetraone or C2-QBINOL 2. Red solid; 13% yield; vmax(neat)
28 33 4
C H O Si requires 461.2143.
2
941, 2866, 1660, 1611, 1573, 1507, 1463, 1416, 1383, 1295, 1238,
ꢁ
1
1
062, 999, 882, 832, 796, 732, 684 cm
CH) SiO), 1.27e1.40 (6H, m,
SiO), 4.10e4.19 (2H, m, OCH CH O), 4.33e4.42
CH O), 6.87 (2H, d, J 10.2 Hz, 2CH ]CH ), 7.02
2H, d, J 10.2 Hz, 2CH ]CH ), 7.33 (2H, d, J 9.2 Hz, Ar), 7.46 (2H, s,
H 3
; d (300 MHz, CDCl )
Acknowledgements
1
2
.00e1.05 (36H, m, 2ꢂ (Me
2
3
ꢂMe
2
CH)
3
a
H
b
a b
H
This research was supported by Mahidol University. Scholarship
supports from the Development and Promotion of Science and
Technology Talents Program (DPST) for K.W. and from the Center
for Innovation in Chemistry: Postgraduate Education and Research
Program in Chemistry (PERCH-CIC) for N.B. are gratefully
acknowledged.
(
(
2H, m, OCH
a
H
b
a
H
b
a
b
a
b
Ar), 7.48 (2H, d, J 9.4 Hz, Ar), 7.92 (2H, d, J 9.4 Hz, Ar), 8.41 (2H, d, J
.2 Hz, Ar); (75 MHz, CDCl ) 12.9, 17.9, 73.2, 109.3, 120.4, 120.7,
24.5, 125.2, 126.6, 128.7, 129.4, 132.2, 133.3, 134.6, 134.8, 135.5,
9
1
d
C
3
þ
140.7, 157.3, 158.4, 185.4, 187.0; HRMS (ESI): MH , found 917.3902.
C
56 61 8 2
H O Si requires 917.3899.
References and notes
4
.8.3. 13,18-Bis((triisopropylsilyl)oxy)-3,4-dihydro-2H-benzo[5,6]
dioxonine-
phenanthro[2,1-f]benzo[5,6]phenanthro[1,2-h][1,5]
,11,20,23-tetraone or C3-QBINOL 3. Red solid; mp 100e103 C; 23%
yield; vmax(neat) 2925, 2865, 1662, 1611, 1574, 1512, 1462, 1416,
1
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8
4
2
ꢁ
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1380, 1298, 1242, 1059, 1003, 930, 883, 833, 793, 687 cm
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H
1
(
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