Oligo(3,6-phenanthrene ethynylenes): Synthesis, characterization, and photoluminescence

Article abstract of DOI:10.1021/jo302825r

A series of highly fluorescent, oligo(3,6-phenanthrene ethynylenes) (F1-F7) were synthesized, and their photophysical behavior was systematically investigated. They emitted light with highly emissive quantum yields, up to 0.92. Emissive wavelengths of these compounds relied on the number of phenanthrene blocks existing in the oligomers. Red-shifted emissions were observed as the number of phenanthrenes increased. On the basis of theoretical calculations, helical structures could be formed for F4-F7, indicating that the excimer emissions might be observed for F4-F7 due to the intramolecular π-π stackings of phenanthrenes in the helical structures. However, excimer emissions were only observed for F5-F7 in dilute cyclohexane and for F6 and F7 in dilute methylene chloride, respectively. No excimer emission was observed for F4-F7 in dilute tetrahydrofuran due to the degree of solvation.

Full text of DOI:10.1021/jo302825r

Article
pubs.acs.org/joc
Oligo(3,6-phenanthrene ethynylenes): Synthesis, Characterization,
and Photoluminescence
Jichao Li, Gongfang Hu, Ningning Wang, Tao Hu, Qiaodong Wen, Ping Lu,* and Yanguang Wang*
Department of Chemistry, Zhejiang University, Hangzhou 310027, People’s Republic of China
*
S Supporting Information
ABSTRACT: A series of highly fluorescent, oligo(3,6-
phenanthrene ethynylenes) (F1−F7) were synthesized, and
their photophysical behavior was systematically investigated.
They emitted light with highly emissive quantum yields, up to
0
.92. Emissive wavelengths of these compounds relied on the
number of phenanthrene blocks existing in the oligomers. Red-
shifted emissions were observed as the number of phenan-
threnes increased. On the basis of theoretical calculations,
helical structures could be formed for F4−F7, indicating that
the excimer emissions might be observed for F4−F7 due to the
intramolecular π−π stackings of phenanthrenes in the helical
structures. However, excimer emissions were only observed for
F5−F7 in dilute cyclohexane and for F6 and F7 in dilute
methylene chloride, respectively. No excimer emission was observed for F4−F7 in dilute tetrahydrofuran due to the degree of solvation.
INTRODUCTION
Scheme 1. Structures of Oligomers F1−F7
■
In 1987, the first organic light-emitting diode device was
designed by Tang and Van Slyke at Eastman Kodak. Over the
1
past three decades, vast quantities of investigations have been
made on developing new materials and optimizing device
architectures to realize the full-color, flat-panel display with
2
−4
improved efficiency and lifetime.
There was an upsurge of
interest in research into polymer electroluminescence since
Burroughes and co-workers reported a highly efficient green
light-emitting polymer based device using 100 nm thick films of
5
poly(p-phenylenevinylene) (PPV). Since then, conjugated
polymers and oligomers based on various aromatic building blocks
have received considerable attention, owing to their intriguing
photoluminescent (PL) and electroluminescent (EL) properties as
improve optoelectronic performance. The oligo(3,6-phenanthrene
ethynylenes) were analogously constructed with respect to the fact
that phenanthrene is rigid and highly fluorescent. From a synthetic
point of view, the phenanthrene moiety can be easily modified at its
3,6-positions or 9,10-positions of the phenanthrene ring through
covalent bonding, while the reactivity of the 2,7-positions is
relatively poor. Thus, 3,6-positions of phenanthrene were chosen to
construct the chain of the oligomers for a relatively stretched
configuration and an efficient conjugation length in which the
undesirable optical defects arising from the dispersed molecular size
could be prevented. Meanwhile, the 9,10-positions of phenanthrene
were intentionally substituted by two alkoxy groups so as to increase
the product solubility as well as to serve as the electron donors in
these structures. Therefore, these designed oligomers would
combine the merits of well-defined structures and superior chemical
2,6,7
well as their promising applications in the field of OLEDs.
Fluorophores, with high quantum yields, a good range of color, and
favorable hole/electron mobilities, were introduced to the
conjugated polymers in order to gain novel emitters that can
8−10
drastically improve the performance of OLEDs.
Phenanthrene and its derivatives have been extensively studied
and developed as the desired blue light-emitting materials due to
1
1−16
their specific optical and electrochemical properties.
Furthermore, it has been demonstrated that the thermal stability
or glass-state durability of materials could be significantly
improved when phenanthrene was integrated in the core
1
7
structures. Previously, we introduced fluorene or pyrene
moieties into the backbone of the acetylene-linked carbazole
oligomers and investigated the effects of chemical structure on
18−21
the electronic, photonic, and morphological properties.
Encouraged by these results, we synthesized the seven oligo(3,6-
Received: December 31, 2012
phenanthrene ethynylenes) F1−F7 (Scheme 1) in order to
©
XXXX American Chemical Society
A
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a
Scheme 2. Synthesis of F1−F7
a
Reagents and conditions: (a) Br , benzoyl peroxide, hν, PhNO , 60 °C; (b) Na S O , K CO , Bu NBr, n-C H Br, H O/THF, room temperature,
2
2
2
2
8
2
3
4
8
17
2
4
8 h; (c) TMSCCH, CuI, Pd(PPh ) , Ph P, NEt , N , reflux; (d) KF, MeOH/THF, N , reflux; (e) CuI, Pd(PPh ) , Ph P, NEt , N , reflux.
3 4 3 3 2 2 3 4 3 3 2
2
2
purities possessed by small molecules and might be used as models for
understanding the fluorescent structure−property relationship in detail.
a suitable amount. As the mechanism of this radical
bromination has been seldom discussed in the literature, we
postulated a possible mechanism for this transformation
(Scheme S1, Supporting Information). Treatment of 2a,b with
Na S O followed by K CO , 1-bromooctane, and Bu NBr in the
RESULTS AND DISCUSSION
■
(
2
2
8
2
3
4
Synthesis and Characterization of Oligomers. Oligo-
3,6-phenanthrene ethynylenes) F1−F7 were synthesized from
presence of H O/THF (1/1 v/v) for 48 h at room temperature
2
afforded 3a,b in 45% and 48% yields, respectively. The Pd/Cu-
catalyzed coupling of 3a as well as 3b and ethynyltrimethylsilane
provided 4a,c in 90% and 89% yields, respectively. When the
ratio of 3b to ethynyltrimethylsilane was changed to 1.1/1, 4b
was prepared in 80% yield. Subsequent deprotection of 4a,c with
phenanthrene-9,10-dione (1) as the starting material, and the
Pd/Cu-catalyzed Sonogashira coupling strategy was used to
build the ethylnylene-linked molecules (Scheme 2). Free radical
bromination of 1 afforded 2a,b in 68% and 79% yields,
respectively, when the molar ratio of the bromine was used in
B
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Figure 1. UV spectra of F1−F7 in CH (left), DCM (middle), and THF (right), measured at 1 × 10−5 mol/L.
a
KF generated 5a,c in 95%, and 93% yields, respectively. A similar
Sonogashira coupling was performed between 4b and 5a to
produce 6a, which was directly desilylated into 6b in a yield of
Table 1. UV Absorption Data of F1−F7
1
λ
abs, nm (ε, M− cm−1
)
CH
DCM
THF
68%. 6c and 7a could be prepared by couplings between 3b and
F1 256, 272, 293,
256, 271, 294,
305
256 (4800), 271 (2000), 293 (1000),
306 (800)
5a as well as between 3b and 5c in 73% and 75% yields,
3
04
F2 253, 348, 369,
84
respectively. 8a was prepared from the coupling between 6b and
a in 60% yield. 9,10-Bis(octyloxy)phenanthrene (F1) was
254, 351, 372
252 (5500), 349 (3200), 370 (3000)
7
3
directly synthesized in 49% yield by a procedure similar to that
used to prepare 3a,b. Finally, F2−F7 were prepared via a
Sonogashira coupling reaction. Thus, dropwise addition of 5a
into 3a in the presence of Pd(0)/CuI/PPh under N afforded a
F3 253, 336, 385,
253, 338, 379,
392
253 (12200), 336 (7600), 380 (5800),
395 (3800)
392
F4 253, 277, 291,
254, 273, 293,
333, 357, 395
252 (10100), 271 (8200), 288 (7000),
330 (6300), 354 (6000), 396 (3100)
3
33, 355, 394
F5 252, 281, 293,
41, 377, 395
3
2
254, 281, 296,
343, 380, 398
252 (11300), 281 (8200), 294 (8500),
339 (7800), 378 (5900), 396 (4200)
white solid in 79% yield, which was demonstrated afterward to be
3
23
F2. F3 was synthesized by a similar procedure in 72% yield after
separation. Coupling between 6b and 6c, 5a and 7a, 8a and 5a, and
F6 251, 285, 339,
253, 286, 340,
400
252 (9200), 287 (7500), 340 (6700),
399 (3100)
397
F7 251, 287, 343,
251, 289, 345,
404
252 (10300), 288 (9400), 344 (9000),
400 (3400)
6
b and 7a furnished F4−F7 in yields of 65%, 61%, 56%, and
3
99
52%, respectively. The structures of oligomers F1−F7 were char-
aMeasured at 1 × 10−5 mol/L in CH, DCM and THF, respectively.
1 13
acterized by H and C NMR spectroscopy and HRMS or MALDI-
TOF MS.
Photophysical Properties of Oligomers. The synthesized
oligomers F1−F7 are soluble in common solvents such as
acetone, dichloromethane, tetrahydrofuran, cyclohexane, and
toluene but basically insoluble in polar solvents such as alcohols,
acetonitrile, and water. The photophysical behavior of these
compounds has been examined by measuring their absorption
and fluorescence spectra in three different solvents, cyclohexane
appeared in dilute CH solution in comparison with the
absorption bands at about 250 nm. A similar situation was
observed for these oligomers in DCM and THF, respectively.
Emissive spectra of the oligomers in dilute CH, DCM, and
THF are displayed in Figure 2, while the emissive data are
summarized in Table 3. The vibrational emissions for F1−F4
were assigned to the locally excited (LE) emissions of these
oligomers. In dilute CH solutions (Figure 2, left), regular red-
shifted emissions were observed from F1 to F4. Emissive
wavelengths of F1 (382 nm), F2 (395 nm), F3 (419 nm), and F4
(
CH), tetrahydrofuran (THF), and dichloromethane (DCM).
The absorption spectra of the oligomers in dilute CH, DCM,
and THF are shown in Figure 1, while the absorption parameters
are summarized in Table 1. Oligomers F1−F7 absorbed strongly
at about 250 nm with a weak maximum absorption band in the
range of 300−400 nm. The maximum absorption band can be
ascribed to a π−π* transition of the conjugated backbone. A
trend of red-shifted absorption was exhibited in the absorption
spectra of F1−F7. The maximum absorption wavelengths of
F1−F3 shifted regularly from 359 to 369 to 379 nm in CH,
respectively, resulting from the significant elongation of the
conjugated structure. For F1−F3, the accumulation of
phenanthrene units extended the conjugated system as well as
reduced the energy gap between the HOMO and LUMO, which
was supported by theoretical calculations through the semi-
empirical PM3 method of Gaussian 03 by simplification of
octyloxy into methoxy (Table 2). Nevertheless, this trend was
discontinuous. A nonlinear relationship was observed from F4 to
F7, as no significantly red-shifted absorption was recorded for
F4−F7 that was further confirmed by the calculated energy gaps
between the HOMO and LUMO of F4−F7 in either zigzag or
helical structures (Table 2). However, an increasing trend in
molar absorptivity at the maximum absorption bands of F1−F7
(
430 nm) indicated an effective elongation of conjugation
through the accumulation of phenanthrene blocks. For F5−F7,
the intensity of the LE emission became weaker and structureless
emissions at lower energy appeared. The maximum emission
wavelengths were recorded as 441, 446, and 450 nm for F5−F7,
respectively (Figure 2, left). By changing CH to DCM, structureless
emissions were observed for F6 and F7 only (Figure 2, middle). No
structureless emission was seen for F5−F7 in dilute THF solutions
(Figure 2, right). According to the literature, the structureless
emissions of F5−F7 in CH and F6 and F7 in DCM could be
assigned to the intramolecular excimer emission of two
24
phenanthracene rings.
The concentration effect of F1−F7 on emission spectra was also
investigated by fluorescence spectroscopy (Figures S54 and S55,
Supporting Information). F1 could not form an excimer even at 10−
mol/L, while intermolecular excimers came into existence for F2−F5
3
−4
at 10 mol/L. F6 and F7 could form intramolecular excimers even at
the 10− mol/L level in CH solutions.
6
All oligomers were highly fluorescent in both the solution and solid
states. The PL quantum yields of the oligomers were measured in
C
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Table 2. Calculated Data for F1−F7
a
a
zigzag
helical
E, eV
HOMO, eV
LUMO, eV
Eg, eV
E, eV
HOMO, eV
LUMO, eV
Eg, eV
F1
F2
F3
F4
F5
F6
F7
−0.63
0.98
2.59
4.19
5.80
7.41
9.02
−8.69
−8.45
−8.39
−8.37
−8.37
−8.36
−8.36
−0.69
−1.11
−1.24
−1.29
−1.32
−1.34
−1.35
8.00
7.34
7.15
7.08
7.05
7.02
7.01
4.12
5.58
7.18
8.73
−8.42
−8.43
−8.35
−8.44
−1.31
−1.36
−1.29
−1.42
7.11
7.07
7.06
7.02
a
Calculated via the semiempirical PM3 method of Gaussian 03.
Figure 2. FL spectra of oligomers of F1−F7 in CH (left), DCM (middle), and THF (right), measured at 1 × 10−5 mol/L and excited by the maximum
excitation wavelength.
a
Table 3. Emission Data of Oligomers
CH
DCM
THF
film
b
λex, nm
λem, nm
λex, nm
λem, nm
λex, nm
λem, nm
Φ
λex, nm
λem, nm
F1
F2
F3
F4
F5
F6
F7
305
366
368
354
342
345
344
362, 382, 402
376, 395
396, 419
405, 430
409, 441
420, 446
421, 450
307
370
375
379
378
345
347
368, 389, 403
384, 402
402, 428
411, 434
410, 435
420, 452
306
369
371
376
376
378
349
368, 386, 401
381, 404
400, 423
408, 433
410, 436
410, 436
411, 438
0.05
0.41
0.54
0.91
0.92
0.80
0.72
351
375
385
400
408
411
400
387, 406
406, 428
449
451
462
463
428, 461
471
a
Measured at 1 × 10−5 M in CH, DCM, and THF, respectively. Measured in THF solutions using DPA as a standard.
b
dilute THF solutions by using 9,10-bis(phenylehynyl)anthracene
25
(
DPA, Φ = 1.0 in cyclohexane ) as a standard. As shown in Table 3,
the quantum yields of F2−F7 (0.41−0.92) were much higher than
that of F1 (0.05) and gradually increased from 0.41 (F2)to0.92(F5)
as increments of phenanthrene blocks. However, the quantum yields
were determined to be 0.80 and 0.72 for F6 and F7, respectively.
In thin films, F1 and F2 emitted light at 387 and 428 nm with
shoulder peaks at lower energy bands (Figure 3). In contrast,
F3−F7 exhibited a broader red-shifted emission from 449 to 471 nm
owing to the extension of phenanthrene blocks. The emissive
wavelengths bathochromatically shifted about 10−20 nm in the solid
state in comparison with those in dilute THF solutions, which was
probably because they were prone to close, face-to-face π−π
stacking that led to aggregates and/or excimer formation of
phenanthrene rings in the solid state.
In order to get a good insight into the absorption and emissive
properties of these oligomers, theoretical calculations through
the semiempirical PM3 method of Gaussian 03 by
simplification of octoxy into methoxy were carried out, and the
results are summarized in Table 2. Although the dispersion-
corrected hybrid functionals should be used for precise
Figure 3. Emissive spectra of F1−F7 in thin films, excited by its
maximum excitation wavelength.
2
6
27
calculations, they is too expensive to allow calculation of
these oligomers. Intramolecular excimer formation could be
explained by the flexible backbone of the oligomers. The 120°
D
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Figure 4. Conformations of F4−F7: zigzag vs helical.
bond angle at the 3- and 6-positions of phenanthrene was suitable
to provide a cross-cover overlap, which led to the formation of
intramolecular excimers and the resulting red-shifted emission.
On the basis of theoretical calculations, F4 should start to have
excimer emission because it has a perfectly parallel stacking of the
two terminal phenanthrenes (Figure 4). In comparison with the
potential energy of F4 in the zigzag conformer, intramolecular
π−π interactions arising from the stacking of phenanthrenes
caused F4 in the helical conformer to possess a lower potential energy
with an energy difference of 0.07 eV. Similarly, F5−F7 released their
potential energies by the formation of helical conformers to the
degree of 0.22, 0.23, and 0.29 eV, respectively. Meanwhile, the
average screw pitch was determined to be about 5.0 Å.
In dilute solution, solvation existed. The insertion of solvent
molecules into the middle of the two stacking phenanthrenes
brought about a twisted helical conformation. Thus, the perfectly
helical structure of F4 was damaged even in dilute CH solution,
which was the typical nonpolar solvent. As a result, the
intramolecular excimer emission of F4 in dilute CH solution
could not be observed. As the solvent polarity increased, the
degree of solvation increased. Excimer emission of F5 in dilute
DCM solution disappeared. When the solvent was changed to
THF, no excimer emissions were detected, even for F7.
The results, obtained through inspecting the absorption and
emissive spectra of these pure oligomers in dilute solutions,
demonstrated a certain fluorescent structure−property relation-
ship of these oligomers. Red-shifted emissions and increased
quantum yields were detected for F1−F5. Meanwhile, helical
structures of F4−F7 could be formed due to the inherent
structural factor, which was supported by theoretical calculations.
It was also evidenced by the intramolecular excimer emissions of
F5−F7 in dilute cyclohexane and F6 and F7 in dichloromethane.
Further, these oligomers presented high quantum yields and
could possibly be used as light-emitting materials in optoelec-
tronic devices.
EXPERIMENTAL SECTION
■
General Methods. Unless otherwise stated, all chemicals were
purchased from commercial suppliers and used without further
purification. Tetrahydrofuran and toluene were distilled from sodium/
benzophenone. Dichloromethane was distilled from calcium hydride.
Cyclohexane was distilled under an N atmosphere. Yields reported are
2
isolated yields. NMR spectra were obtained at 400 or 500 MHz for
1
13
H NMR and 100 or 125 MHz for C NMR in CDCl . Chemical shifts
3
are reported in ppm using either tetramethylsilane or the residual CDCl3
as standard. Flash column chromatography was performed employing
2
00−300 mesh silica gel. Thin-layer chromatography (TLC) was
performed on silica with fluorescence at 254 nm.
-Bromo-9,10-bis(octyloxy)phenanthrene (3a). To a solution
3
CONCLUSION
■
of 3-bromophenanthrene-9,10-dione (2a; 5.72 g, 20 mmol) in THF
In summary, a series of well-defined oligo(3,6-phenanthrene
ethynylenes) have been synthesized and fully characterized.
(150 mL) were added Na S O (11.5 g, 60 mmol) and H O (150 mL),
2
2
8
2
and the resulting solution was stirred for 15 min. Then, K CO
2 3
E
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(
6
8.28 g, 60 mmol), TBAF (0.64 g, 2 mmol), and 1-bromooctane (11.5 g,
0 mmol) were sequentially added into the solution. After the solution
was purged with nitrogen for 10 min, it was stirred under nitrogen for
8 h at room temperature. Then the solution was poured into H O and
0.8 Hz, 1H), 7.67−7.55 (m, 2H), 4.24−4.17 (m, 4H), 3.20 (s, 1H),
1.97−1.84 (m, 4H), 1.58−1.53 (m, 4H), 1.38−1.31 (m, 16H), 0.92−
0.89 (m, 6H). 13C NMR (100 MHz, CDCl ): δ 144.6, 143.2, 130.2,
3
4
130.0, 128.8, 128.6, 128.4, 127.4, 127.3, 126.3, 122.9, 122.7, 84.7, 74.0,
32.2, 30.8, 29.9, 29.7, 26.6, 23.0, 14.5. HRMS (EI): calcd for C H O
2
2
extracted with CH Cl (4 × 30 mL). The organic layer was combined,
dried over anhydrous MgSO , and filtered. The filtrate was evaporated
2
2
32 42
+
4
458.3185 (M ), found 458.3168.
under reduced pressure. The residue was purified through column
3,6-Diethynyl-9,10-bis(octyloxy)phenanthrene (5c). The pro-
chromatography (silica gel, hexane/dichloromethane as eluent) to give 3a
cedure was analogous to that described for 5a. 5c was obtained (0.89 g,
1
1
(
4.60 g, 45% yield) as a colorless oil. H NMR (400 MHz, CDCl ): δ 8.76
93% yield) as a white solid. Mp: 77−78 °C, H NMR (400 MHz,
3
(
d, J = 1.6 Hz, 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.25 (dd, J = 7.6, 1.6 Hz, 1H),
CDCl ): δ 8.75 (s, 2H), 8.17 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.4 Hz, 2H),
3
8
4
1
1
9
.12 (d, J = 8.4 Hz, 1H), 7.70 (dd, J = 8.8, 1.6 Hz, 1H), 7.67−7.59 (m, 2H),
4.18 (t, J = 6.6 Hz, 4H), 3.21 (s, 2H), 1.91−1.85 (m, 4H), 1.56−1.51
1
3
.21 (m, 4H), 1.94−1.88 (m, 4H), 1.63−1.52 (m, 4H), 1.39−1.33 (m,
(m, 4H), 1.37−1.30 (m, 16H), 0.90 (t, J = 6.4 Hz, 6H). C NMR
1
3
6H), 0.94−0.88 (m, 6H). C NMR (100 MHz, CDCl ): δ 144.0, 143.2,
(100 MHz, CDCl ): δ 144.2, 130.4, 130.2, 128.0, 127.3, 122.8, 119.9,
3
3
35.6, 132.0, 130.7, 130.2, 129.1, 127.7, 127.6, 126.3, 124.4, 122.9, 122.7,
84.5, 78.1, 74.1, 32.2, 30.8, 29.8, 29.7, 26.6, 23.0, 14.4. HRMS (EI): calcd
+
1.8, 74.0, 73.9, 32.2, 30.8, 29.9, 29.7, 26.6, 23.1, 14.5. HRMS (EI): calcd for
for C H O 482.3185 (M ), found 482.3183.
34
42
2
+
C H BrO 512.2290 (M ), found 512.2302.
3-((9,10-Bis(octyloxy)phenanthren-3-yl)ethynyl)-6-ethynyl-
9,10-bis(octyloxy)phenanthrene (6b). To a solution of 4b (0.608 g,
1 mmol) in dry triethylamine (100 mL) were added tetrakis-
(triphenylphosphine)palladium (3.5 mg, 0.005 mmol), cuprous iodide
(10 mg, 0.05 mmol), and triphenylphosphine (5 mg, 0.02 mmol). After
the solution was purged with nitrogen for 10 min, 5a (0.456 g, 1.0
mmol) in 10 mL of triethylamine was added dropwise though a constant
pressure dropping funnel in 10 min. Then the solution was refluxed
under nitrogen for 8 h. The reaction mixture was filtered, and the filtrate
was evaporated under reduced pressure. The residue was purified by
column chromatography (silica gel, hexane/DCM as eluent) to afford
30
41
2
3,6-Dibromo-9,10-bis(octyloxy)phenanthrene (3b). The pro-
cedure was analogous to that described for 3a, but 3,6-dibromophenan-
threne-9,10-dione (2b; 7.26 g, 20 mmol) was used instead of 2a. Thus,
3
1
b was obtained (5.43 g, 48% yield) as a white solid. Mp: 63−64 °C. H
NMR (400 MHz, CDCl ): δ 8.64 (d, J = 1.6 Hz, 2H), 8.09 (d, J = 8.8 Hz,
3
2
H), 7.71 (dd, J = 8.8, 1.6 Hz, 2H), 4.17 (t, J = 6.8 Hz, 4H), 1.92−1.85
(
m, 4H), 1.57−1.53 (m, 4H), 1.31−1.28 (m, 16H), 0.92−0.89 (m, 6H).
1
3
C NMR (100 MHz, CDCl ): δ 143.5, 130.8, 129.2, 129.1, 125.7, 124.5,
3
120.6, 74.1, 32.2, 30.8, 29.8, 29.7, 26.6, 23.0, 14.4. HRMS (EI): calcd for
+
C H Br O 590.1395 (M ), found 590.1413.
30
40
2
2
(
(9,10-Bis(octyloxy)phenanthren-3-yl)ethynyl)trimethylsilane
6a. After removal of TMS by KF, 6b was obtained (0.670 g, 68% yield) as
1
(
0
(
4a). To a solution of 3a (1.02 g, 2 mmol), cuprous iodide (9 mg,
a slightly yellow solid. Mp: 79−80 °C. H NMR (400 MHz, CDCl ): δ
3
.05 mmol), Pd(PPh ) (5.5 mg, 0.005 mmol), and triphenylphosphine
5.2 mg, 0.02 mmol) in dry triethylamine (100 mL) was added
ethynyltrimethylsilane (0.22 g, 2.2 mmol). The mixture was refluxed
under nitrogen for 8 h and then filtered. The filtrate was evaporated
under reduced pressure. The residue was purified through column
8.91 (s, 1H), 8.86 (s, 1H), 8.83 (s, 1H), 8.70−8.68 (m, 1H), 8.27−8.21
(m, 3H), 8.18 (d, J = 8.4 Hz, 1H), 7.83−7.80 (m, 2H), 7.73 (dd, J = 8.4,
1.2 Hz, 1H), 7.64−7.62 (m, 2H), 4.24−4.18(m, 8H), 3.21(s, 1H), 1.92−1.89
3
4
13
(m, 8H), 1.57−1.54 (m, 8H), 1.3−1.31 (m, 32H), 0.92−0.89 (m, 12H). C
NMR (100 MHz, CDCl ) δ144.5, 144.4, 144.1, 143.4, 132.5, 132.4, 130.3,
3
chromatography (silica gel, hexane/DCM as eluent) to give pure 4a
0.95 g, 90% yield) as a colorless oil. H NMR (400 MHz, CDCl ): δ
130.2, 130.1, 129.80, 129.75, 129.7, 128.9, 128.8, 127.4, 126.7, 126.6, 126.3,
1
(
122.9, 122.8, 91.4, 90.7, 84.6, 78.1, 74.1, 74.0, 32.2, 30.9, 30.8, 29.9, 29.7, 26.6,
3
+
8
8
2
1
.77 (s, 1H), 8.61 (dd, J = 7.6, 1.6 Hz, 1H), 8.24 (dd, J = 7.2, 2.0 Hz, 1H),
.16 (d, J = 8.5 Hz, 1H), 7.67 (dd, J = 8.4, 1.2 Hz, 1H), 7.64−7.57 (m,
H), 4.23−4.17 (m, 4H), 1.97−1.84 (m, 4H), 1.57−1.54 (m, 4H),
2
3.0, 14.5. HRMS (EI): calcd for C H O 914.6213 (M ), found 914.6229.
64
82
4
3
-((9,10-Bis(octyloxy)phenanthren-3-yl)ethynyl)-6-bromo-
9,10-bis(octyloxy)phenanthrene (6c). 3b (1.0 g, 1.7 mmol) and 5a
(0.458 g, 1.0 mmol) were used for coupling. After purification by
column chromatography (silica gel, hexane/DCM as eluent), 6c (0.71 g,
13
.38−1.26 (m, 16H), 0.92−0.88 (m, 6H), 0.32 (s, 9H). C NMR (100
MHz, CDCl ) δ 151.4, 151.0, 142.3, 140.6, 131.5, 128.0, 127.2, 126.9,
3
1
1
23.2, 120.5, 120.4, 119.9, 85.1, 40.6, 32.1, 30.3, 29.6, 24.0, 22.9, 14.4.
HRMS (EI): calcd for C H O Si 530.3580 (M ), found 530.3579.
73% yield) was obtained as a slightly yellow solid. Mp: 60−61 °C. H
+
35
50
2
NMR (400 MHz, CDCl ): δ 9.03 (s, 1H), 8.94 (s, 1H), 8.81 (s, 1H), 8.72 (d,
3
(
(6-Bromo-9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-
J = 8.8 Hz, 1H), 8.28−8.23 (m, 3H), 7.98 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.8
trimethylsilane (4b). When the ratio of 3b to ethynyltrimethylsilane
was changed to 1.1/1, 4b was obtained (0.972 g, 80% yield) as a
Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.67−7.65 (m, 2H), 4.31−4.14 (m, 8H),
1
.97−1.91 (m, 8H), 1.61−1.57 (m, 8H), 1.40−1.34 (m, 32H), 0.95−0.92
colorless oil. It could also be obtained as a byproduct in the synthesis of
a,c in a certain amount. H NMR (400 MHz, CDCl ): δ 8.73 (s, 1H),
13
(m, 12H). C NMR (100 MHz, CDCl ): δ 144.6, 143.4, 138.2, 130.3, 130.1,
3
1
4
8
(
1
(
1
3
3
128.9, 128.6, 127.7, 127.5, 126.3, 124.3, 123.1, 122.9, 122.8, 119.2, 74.11,
.66 (s, 1H), 8.15 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 8.8 Hz, 1H), 7.71−7.67
7
4.07, 32.2, 30.89, 30.88, 29.90, 29.88, 29.71, 29.69, 26.65, 26.63, 23.1, 14.5.
m, 2H), 4.21−4.16 (m, 4H), 1.91−1.87 (m, 4H), 1.57−1.53 (m, 4H),
+
HRMS (EI): calcd for C H BrO 968.5318 (M ), found 968.5311.
6
2
81
4
13
.36−1.31 (m, 16H), 0.90 (t, J = 6.4 Hz, 6H), 0.33 (s, 9H). C NMR
6
,6′-(9,10-Bis(octyloxy)phenanthrene-3,6-diyl)bis(ethyne-
2,1-diyl)bis(3-bromo-9,10-bis(octyloxy)phenanthrene) (7a). 3b
1.8 g, 3.05 mmol) and 5c (0.482 g, 1.0 mmol) were used for coupling.
100 MHz, CDCl ): δ 144.2, 143.5, 130.6, 130.5, 130.2, 129.8, 128.9,
3
27.5, 127.0, 125.8, 124.5, 122.7, 120.9, 120.7, 105.8, 95.4, 74.1, 74.0,
2.2, 30.8, 29.8, 29.7, 26.6, 23.0, 14.5, 0.4. HRMS (EI): calcd for
(
After purification by column chromatography (silica gel, hexane/DCM
+
C H BrO Si 608.2685 (M ), found 608.2657.
3
5
(
49
2
as eluent), 7a (1.13 g, 75% yield) was obtained as a slightly yellow solid.
1
9,10-Bis(octyloxy)phenanthrene-3,6-diyl)bis(ethyne-2,1-
Mp: 82−83 °C. H NMR (400 MHz, CDCl ): δ 8.98 (s, 2H), 8.82
3
diyl)bis(trimethylsilane) (4c). The procedure was analogous to that
(
d, J = 4.4 Hz, 4H), 8.27−8.22 (m, 4H), 8.10 (d, J = 8.4 Hz, 2H), 7.86 (d,
described for 4a. Thus 4c was obtained (1.10 g, 89% yield) as a colorless
oil. H NMR (400 MHz, CDCl ): δ 8.74 (s, 2H), 8.15 (d, J = 8.4 Hz,
J = 8.4 Hz, 4H), 7.72 (d, J = 8.8 Hz, 2H), 4.26−4.21 (m, 12H), 1.96−
1
3
1.92 (m, 12H), 1.62−1.58 (m, 12H), 1.48−1.35 (m, 48H), 0.97−0.92
2
1
(
1
H), 7.67 (d, J = 8.4 Hz, 2H), 4.19 (t, J = 6.4 Hz, 4H), 1.93−1.86 (m, 4H),
13
(
m, 18H). C NMR (125 MHz, CDCl ): δ 144.3, 144.1, 143.7, 132.5,
3
.57−1.51 (m, 4H), 1.37−1.31 (m, 16H), 0.92−0.88 (m, 6H), 0.33
1
1
1
2
32.4, 132.3, 132.2, 130.5, 130.4, 130.2, 130.1, 130.0, 129.9, 128.93,
28.89, 128.8, 128.3, 127.7, 126.7, 126.7, 125.9, 124.5, 122.9, 121.1,
21.0, 120.8, 91.3, 91.0, 74.2, 74.1, 32.23, 32.21, 30.87, 30.83, 29.88,
13
s, 18H). C NMR (100 MHz, CDCl ): δ 144.2, 130.4, 129.9, 128.0, 127.0,
3
22.6, 120.8, 105.9, 95.2, 74.1, 32.2, 30.8, 29.8, 29.7, 26.6, 23.0, 14.5, 0.4.
HRMS (EI): calcd for C H O Si 626.3975 (M ), found 626.3973.
3
a (1.06 g, 2 mmol) and KF (500 mg) in methanol (100 mL) was
refluxed under nitrogen for 2 h. The solvent was then removed, and the
crude product was purified by column chromatography (silica gel,
hexane/DCM as eluent) to afford 5a (0.87 g, 95% yield) as a colorless
oil. H NMR (400 MHz, CDCl ): δ 8.80 (s, 1H), 8.63−8.54 (m, 1H),
.25 (dd, J = 7.8, 1.4 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 7.69 (dd, J = 8.4,
+
40
58
2 2
9.87, 29.85, 29.70, 29.68, 29.67, 26.63, 26.60, 23.1, 23.0, 14.48, 14.47.
-Ethynyl-9,10-bis(octyloxy)phenanthrene (5a). A solution of
+
HRMS (EI): calcd for C H Br O 1502.7452 (M ), found 1502.7450.
94
120
2
6
4
3
-((9,10-Bis(octyloxy)phenanthren-3-yl)ethynyl)-6-((6-((6-
(
(6-bromo-9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-9,10-
bis(octyloxy)phenanthren-3-yl)ethynyl)-9,10-bis(octyloxy)-
phenanthren-3-yl)ethynyl)-9,10-bis(octyloxy)phenanthrene
(8a). 7a (0.75 g, 0.5 mmol) and 6b (0.44 g, 0.48 mmol) were used for
coupling. After purification by column chromatography (silica gel,
1
3
8
F
dx.doi.org/10.1021/jo302825r | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
hexane/DCM as eluent), 8a (0.673 g, 60% yield) was obtained as a
9.13 (s, 2H), 8.98 (s, 2H), 8.94 (s, 2H), 8.87 (s, 2H), 8.62 (d, J = 6.4 Hz,
2H), 8.32 (d, J = 8.4 Hz, 2H), 8.16−8.10 (m, 8H), 7.82 (d, J = 8.4 Hz,
2H), 7.83−7.77 (m, 4H), 7.73 (d, J = 8.8 Hz, 2H), 7.53−7.49 (m, 4H),
4.29−4.13 (m, 20H), 2.01−1.91 (m, 20H), 1.64−1.57 (m, 20H), 1.50−
1
sticky oil. H NMR (400 MHz, CDCl ): δ 9.10 (s, 2H), 8.97−8.89
3
(
m, 4H), 8.84 (s, 1H), 8.72 (s, 2H), 8.59 (d, J = 8.8 Hz, 1H), 8.29 (d, J =
8
.4 Hz, 2H), 8.14−8.03 (m, 7H), 7.98 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.4
13
Hz, 2H), 7.82−7.75 (m, 4H), 7.76 (dd, J = 8.8, 3.6 Hz, 2H), 7.70 (dd, J =
1.35 (m, 80H), 0.98−0.94 (m, 30H). C NMR (125 MHz, CDCl ): δ
3
8
4
1
1
1
1
1
1
2
.8, 3.6 Hz, 2H), 7.61 (dd, J = 8.8, 1.6 Hz, 1H), 7.50−7.45 (m, 2H),
144.3, 144.2, 144.1, 143.2, 130.2, 130.0, 129.9, 129.73, 129.69, 129.6,
129.4, 128.6, 128.4, 128.3, 128.2, 128.1, 127.1, 126.8, 126.7, 126.6, 126.5,
126.1, 123.0, 122.8, 122.59, 122.56, 122.4, 121.2, 121.1, 120.9, 120.6,
91.5, 91.2, 91.0, 74.2, 74.0, 73.9, 32.3, 30.9, 29.9, 29.7, 26.6, 23.1, 14.5.
MS (MALDI-TOF): m/z 2258.2.
.29−4.07 (m, 20H), 2.00−1.88 (m, 20H), 1.64−1.56 (m, 20H), 1.43−
13
.37 (m, 80H), 0.97−0.94 (m, 30H). C NMR (125 MHz, CDCl ): δ
3
44.3, 144.2, 144.1, 144.0, 143.5, 143.3, 130.4, 130.3, 130.2, 130.1, 130.0,
29.9, 129.7, 129.6, 129.5, 129.4, 128.7, 128.6, 128.4, 128.3, 128.2, 128.1,
27.5, 127.1, 126.9, 126.8, 126.60, 126.56, 126.4, 126.1, 125.8, 124.3,
22.9, 122.8, 122.7, 122.6, 122.4, 121.3, 121.2, 121.0, 120.9, 120.70,
20.66, 91.5, 91.3, 91.2, 91.0, 74.2, 74.0, 73.9, 32.3, 30.9, 29.9, 29.7, 26.7,
1,2-Bis(6-((6-((9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-
9
(
,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-9,10-bis-
octyloxy)phenanthren-3-yl)ethyne (F6). 8a (0.234 g, 0.1 mmol)
+
and 5a (0.046 g, 0.1 mmol) were used for coupling. After purification by
3.1, 14.5. MS (MALDI-TOF): m/z 2337.6 (M ).
column chromatography (silica gel, hexane/DCM as eluent), F6 (0.152 g,
9
,10-Bis(octyloxy)phenanthrene (F1). The procedure was
analogous to that described for 3a, but phenanthrene-9,10-dione
1; 0.416 g, 2 mmol) was used. After purification by column chromato-
1
5
6% yield) was obtained as a sticky oil. H NMR (400 MHz, CDCl ): δ 9.01
3
(
8
s, 2H), 8.90 (s, 2H), 8.87 (s, 2H), 8.79 (s, 4H), 8.54 (d, J = 6.4 Hz, 2H),
.12 (d, J = 6.8 Hz, 2H), 8.02−7.95 (m, 8H), 7.91 (d, J = 6.4 Hz, 2H), 7.80
(
graphy (silica gel, hexane/DCM as eluent), F1 (0.43 g. 49% yield) was
1
(d, J = 6.4 Hz, 2H), 7.71−7.69 (m, 4H), 7.53−7.51 (m, 4H), 7.36−7.31
obtained as a colorless oil. H NMR (400 MHz, CDCl ): δ 8.68 (d, J =
3
(
1
m, 4H), 4.17−4.09 (m, 24H), 1.93−1.87 (m, 24H), 1.61−1.55(m, 24H),
6
.0 Hz, 2H), 8.32 (dd, J = 8.4, 1.2 Hz, 2H), 7.70−7.63 (m, 4H), 4.27
13
.45−1.35 (m, 96H), 0.95−0.92 (m, 36H). C NMR (125 MHz, CDCl ):
3
(
t, J = 5.6 Hz, 4H), 2.03−1.97 (m, 4H), 1.68−1.62 (m, 4H), 1.50−1.39
13
δ 144.1, 144.0, 143.92, 143.88, 143.85, 143.1, 130.1, 129.9, 129.65, 129.60,
29.5, 129.3, 129.1, 129.0, 128.4, 128.2, 128.1, 127.93, 127.90, 126.8, 126.7,
126.5, 126.3, 126.1, 125.9, 122.8, 122.6, 122.3, 122.1, 121.0, 120.9, 120.8,
(
m, 16H), 1.00−0.97 (m, 6H). C NMR (100 MHz, CDCl ): δ 143.6,
3
1
1
2
30.0, 129.0, 127.0, 126.0, 122.9, 122.6, 74.0, 32.2, 30.9, 29.9, 29.7, 26.7,
+
3.0, 14.5. HRMS: calcd for C H O 434.3185 (M ), found 434.3186.
30
42
2
1
20.6, 91.5, 91.4, 90.9, 74.01, 73.96, 73.92, 73.86, 32.2, 30.9, 30.0, 29.8, 26.7,
1
,2-Bis(9,10-bis(octyloxy)phenanthren-3-yl)ethyne (F2). 3a
23.2, 14.5. MS (MALDI-TOF): m/z 2712.9.
(
0.512 g, 1 mmol) and 5a (0.241 g, 0.5 mmol) were used for coupling.
6
,6′-(9,10-Bis(octyloxy)phenanthrene-3,6-diyl)bis(ethyne-
After purification by column chromatography (silica gel, hexane/DCM
2
,1-diyl)bis(3-((6-((9,10-bis(octyloxy)phenanthren-3-yl)-
as eluent), F2 (0.35 g, 79% yield) was obtained as a white solid. Mp: 60−
ethynyl)-9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-9,10-
bis(octyloxy)phenanthrene) (F7). 6c (0.213 g, 0.22 mmol) and 7a
1
6
8
4
3
1
1
1 °C. H NMR (400 MHz, CDCl ): δ 8.91 (s, 2H), 8.71−8.68 (m, 2H),
3
.28−8.24 (m, 4H), 7.82 (d, J = 8.8 Hz, 2H), 7.67−7.62 (m, 4H), 4.25−
.21 (m, 8H), 1.96−1.89 (m, 8H), 1.62−1.55 (m, 8H), 1.41−1.31 (m,
(
0.150 g, 0.1 mmol) were used for coupling. After purification by
column chromatography (silica gel, hexane/DCM as eluent), F7 (0.165
g, 52% yield) was obtained as a sticky oil. H NMR (400 MHz, CDCl ):
13
1
2H), 0.92−0.89 (m, 12H). C NMR (100 MHz, CDCl ): δ 144.5,
3
3
43.4, 130.3, 129.8, 129.7, 128.8, 128.5, 127.4, 126.7, 126.3, 123.1, 122.8,
δ 8.96 (s, 2H), 8.86 (s, 2H), 8.75 (s, 2H), 8.72 (s, 4H), 8.57 (s, 2H), 8.42
22.8, 120.7, 91.0, 74.1, 32.2, 30.9, 29.9, 29.7, 26.6, 23.0, 14.5. HRMS:
calcd for C H O 890.6213 (M ), found 890.6192.
(
d, J = 8.4 Hz, 2H), 8.09 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H),
7.89 (d, J = 8.4 Hz, 2H), 7.81−7.74 (m, 8H), 7.68−7.63 (m 4H), 7.57
d, J = 8.4 Hz, 2H), 7.43 (dd, J = 6.0, 3.6 Hz, 1H), 7.28 (d, J = 9.2 Hz,
+
62
84
4
3
,3′-(9,10-Bis(octyloxy)phenanthrene-3,6-diyl)bis(ethyne-
,1-diyl)bis(9,10-bis(octyloxy)phenanthrene) (F3). 3a (0.77 g,
.5 mmol) and 5c (0.241 g, 0.5 mmol) were used for coupling. After
(
2
2
4
1
H), 7.22−7.18 (m, 3H), 7.16−7.12 (m, 2H), 7.07−7.04 (m, 2H),
1
.22−4.13 (m, 16H), 4.06−3.95 (m, 12H), 1.96−1.80 (m, 28H), 1.70−
purification by column chromatography (silica gel, hexane/DCM as
eluent), F3 (0.475 g, 72% yield) was obtained as a slightly yellow solid.
13
.56 (m, 28H), 1.52−1.37 (m, 112H), 0.97−0.90 (m, 42H). C NMR
(
125 MHz, CDCl ): δ 143.94, 143.93, 143.88, 143.86, 143.7, 143.6,
3
1
Mp: 62−63 °C. H NMR (400 MHz, CDCl ): δ 8.99 (s, 2H), 8.96
3
143.0, 130.3, 129.7, 129.5, 129.4, 129.3, 129.2, 128.9, 128.8, 128.7, 128.4,
(
s, 2H), 8.73 (d, J = 8.4 Hz, 2H), 8.28 (d, J = 8.4 Hz, 6H), 7.82 (dd, J =
.4, 1.2 Hz, 4H), 7.68−7.63 (m, 4H), 4.28−4.22 (m, 12H), 1.99−1.91
1
1
1
28.1, 128.0, 127.9, 127.7, 126.54, 126.49, 126.4, 126.3, 126.1, 125.9,
25.8, 122.6, 122.3, 122.2, 122.1, 122.1, 121.9, 121.8, 121.6, 121.3, 120.9,
20.79, 120.76, 120.5, 111.7, 92.0, 91.62, 91.59, 91.5, 91.4, 91.0, 74.0,
8
(
m, 12H), 1.65−1.55 (m, 12H), 1.41−1.33 (m, 48H), 0.95−0.91 (m,
13
1
1
1
2
1
8H). C NMR (100 MHz, CDCl ): δ 144.5, 144.3, 143.4, 130.2, 130.1,
3
73.92, 73.86, 73.74, 73.68, 73.6, 32.4, 32.34, 32.29, 31.1, 31.0, 30.9, 30.2,
30.1, 30.0, 29.9, 29.8, 29.8, 26.8, 26.7, 23.11, 23.06, 14.5. MS (MALDI-
TOF): m/z 3170.6.
29.9, 129.8, 129.7, 128.8, 128.5, 128.3, 127.4, 126.7, 126.3, 123.1, 122.9,
22.8, 122.7, 121.1, 120.6, 91.3, 90.8, 74.2, 74.1, 32.2, 30.9, 29.9, 29.7,
6.6, 23.0, 14.5. HRMS: calcd for C H O 1346.9241 (M ), found
346.9246.
,2-Bis(6-((9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-
,10-bis(octyloxy)phenanthren-3-yl)ethyne (F4). 6c (0.300 g,
+
94
122
6
ASSOCIATED CONTENT
1
■
9
*
S
Supporting Information
0.31 mmol) and 6b (0.183 g, 0.2 mmol) were used for coupling. After
Text and figures giving general information, NMR and mass
spectra of intermediates and oligomers, and the concentration
effect of oligomers on excimer formation. This material is
available free of charge via the Internet at http://pubs.acs.org.
purification by column chromatography (silica gel, hexane/DCM as
eluent), F4 (0.234 g, 65% yield) was obtained as a white solid. Mp: 52−
1
5
(
8
7
1
3 °C. H NMR (400 MHz, CDCl ): δ 9.01 (d, J = 4.4 Hz, 4H), 8.90
3
s, 2H), 8.67−8.64 (m, 2H), 8.29 (dd, J = 8.8, 3.2 Hz, 4H), 8.19 (dd, J =
.8, 3.2 Hz, 4H), 7.88 (t, J = 8.8 Hz, 4H), 7.81 (d, J = 8.8 Hz, 2H), 7.57−
.54 (m, 4H), 4.28−4.13 (m, 16H), 2.00−1.86 (m, 16H), 1.63−1.53 (m,
AUTHOR INFORMATION
13
■
6H), 1.41−1.32 (m, 64H), 0.95−0.90 (m, 24H). C NMR (100 MHz,
Corresponding Author
CDCl ): δ 144.5, 144.34, 144.29, 143.3, 137.6, 137.5, 134.2, 134.0,
3
1
1
1
2
32.5, 132.4, 130.2, 130.1, 130.0, 129.9, 129.7, 129.6, 129.0, 128.9, 128.8,
28.44, 128.36, 127.3, 126.8, 126.7, 126.3, 123.02, 122.96, 122.9, 122.8,
22.6, 121.2, 121.1, 120.6, 91.5, 91.2, 90.9, 74.1, 74.0, 32.2, 30.89, 30.85,
*E-mail: pinglu@zju.edu.cn (P.L.); orgwyg@zju.edu.cn (Y.W.).
Fax: (+86) 571-87952543.
+
Notes
9.9, 29.7, 26.6, 14.5. MS (MALDI-TOF): m/z 1826.5 ([M + 23] ).
The authors declare no competing financial interest.
6
,6′-(9,10-Bis(octyloxy)phenanthrene-3,6-diyl)bis(ethyne-
2
9
,1-diyl)bis(3-((9,10-bis(octyloxy)phenanthren-3-yl)ethynyl)-
,10-bis(octyloxy)phenanthrene) (F5). 5a (0.458 g, 1 mmol) and 7a
ACKNOWLEDGMENTS
■
(
0.600 g, 0.4 mmol) were used for coupling. After purification by
column chromatography (silica gel, hexane/DCM as eluent), F5 (0.55 g,
6
This work was supported by the National Natural Science
Foundation of China (Nos. 21272203; J1210042).
1
1% yield) was obtained as a sticky oil. H NMR (400 MHz, CDCl ): δ
3
G
dx.doi.org/10.1021/jo302825r | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
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dx.doi.org/10.1021/jo302825r | J. Org. Chem. XXXX, XXX, XXX−XXX