Synthesis of chrysene derivatives via copper-catalyzed one-pot dimerization of 2-alkynyl-1-acetylbenzenes

Article abstract of DOI:10.1021/jo500182k

An efficient route for highly substituted chrysene derivatives via operationally simple copper-catalyzed one-pot dimerization of 2-alkynyl-1-acetylbenzenes is described.

Full text of DOI:10.1021/jo500182k

Article
pubs.acs.org/joc
Synthesis of Chrysene Derivatives via Copper-Catalyzed One-Pot
Dimerization of 2‑Alkynyl-1-acetylbenzenes
Biao Guo, Liyao Zheng, Lichen Yang, and Ruimao Hua*
Department of Chemistry, Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua
University, Beijing 100084, China
S
* Supporting Information
ABSTRACT: An efficient route for highly substituted
chrysene derivatives via operationally simple copper-catalyzed
one-pot dimerization of 2-alkynyl-1-acetylbenzenes is de-
scribed.
Scheme 1. Synthesis of Chrysene Derivatives via 2-Alkynyl-
1-acetylbenzenes
INTRODUCTION
■
As an important class of polycyclic aromatic hydrocarbons
(PAHs),1 chrysene derivatives are attracting renewed attention
due to their unique electron properties.2,3 With good hole- and
electron-transport capabilities, these compounds can be used as
base molecules for electronic devices such as field-effect
transistors (FETs).4 In addition, they are new candidates for
blue emitters in organic light-emitting diodes (OLEDs) because
of their high fluorescence quantum efficiency.5,6
Traditional procedures for chrysene derivatives usually
required complex starting materials or tedious multistep
reactions but with low yield.3,6−9 Consequently, it is crucial
to find practical and atom-economical synthetic methods for
chrysene derivatives from simple starting materials in materials
chemistry and fine chemical industries. In 1982, Kuznetsov et
al. reported a unique method for chrysene derivatives synthesis
via acid-promoted dimerization of benzopyrylium salts
(Scheme 1a).8 However, this procedure was not synthetically
useful because of its poor chemoselectivity and the difficulty in
preparing benzopyrylium salts.9 In 2007, Liu and co-workers
reported a one-pot approach to synthesize chrysenes via Pt(II)-
catalyzed hydrative dimerization of 2-alkynyl-1-acetylbenzenes
(Scheme 1b).10 Although Liu’s synthetic method is much more
efficient than traditional methods, its substituent scope is
limited (only substrates with R = alkyl are investigated). In
addition, application of the procedure would be impeded by the
costly platinum catalyst.
2-Alkynyl-1-acetylbenzenes are a widely investigated class of
bifunctional substrates11,12 for their convenient synthesis via the
Sonogashira reaction13 and diverse transformations to cyclic
compounds.12 During synthesis of 2-phenylethynyl-1-acetyl-
benzene (3a) from 1-(2-bromophenyl)ethanone (1a) and
ethynylbenzene (2a) under the classical Sonogashira cross-
coupling reaction conditions, we found unexpectedly a small
amount of chrysene derivative (4a), which obviously derived
from dimerization of 3a (Scheme 1c). In view of the promising
applications of chrysene derivatives and our continuing interest
in transition-metal-catalyzed cascade alkyne annulations,14 we
embarked on developing this side reaction as an efficient
method for chrysene derivative synthesis.
Received: January 24, 2014
Published: April 18, 2014
© 2014 American Chemical Society
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RESULTS AND DISCUSSION
Scheme 2. Synthesis of Chrysene Derivatives via 2-(2-
Acetylphenyl)-1-phenylethanone
■
We employed 2-phenylethynyl-1-acetylbenzene (3a) as the
substrate to optimize the reaction conditions. The results are
outlined in Table 1. We initially tried the transformation of 3a
a
Table 1. Optimization of Reaction Conditions
of (arylalkynyl)acetophenones like 3a was not reported in their
catalytic system. However, no desired product 4a was detected
by using diketone 5a as starting material under a CuCl2/NEt3
catalytic system (conditions of entry 10). These results
indicated that diketone 5a is not the crucial intermediate for
the formation of 4a, and the hydrolysis of 3a to 5a in situ may
be a side reaction resulting in the low yield of 4a. Therefore, we
repeated the reaction with the addition of 5.0 equiv of
HC(OEt)3 as dehydrating agent to consume in situ generated
water. Gratifyingly, the yield of 4a was greatly improved (88%,
entry 14), and under either N2 or air atmosphere, the catalytic
system showed almost the same catalytic activity. Other
dehydrating agents such as anhydrous MgSO4 (entry 15) and
4 Å molecular sieves (entry 16) were also examined, and both
of them could improve the yield of 4a under air atmosphere but
showed less efficiency than HC(OEt)3. In addition, CuI also
showed the high catalytic activity in the presence of HC(OEt)3
under either N2 or air atmosphere (entry 17).
With the optimal reaction conditions in hand, we employed
various 2-alkynyl-1-acetylbenzenes to explore the generality of
the dimerization reaction under air atmosphere (Table 2). The
reactions proceeded smoothly by using various substrates 3
having electron-donating groups (EDGs, entries 2−5) or
electron-withdraw groups (EWGs, entries 6−11) at the para-
position of the phenylethynyl group. Entries 2−11 show the
suitability of the reaction with alternation of R2 group. When
the R2 group was an alkyl group such as Me (3b, 42%), n-Pr
(3c, 39%), and t-Bu (3d, 62%), respectively, the reactions gave
the desired product in moderate yields. When R2 was a MeO
group, the corresponding product 4e was obtained in good
yield (70%). The reactions of substrate 3 with EWGs in
phenylethynyl groups such as 4-F-Ph (3f, 53%), 4-Cl-Ph (3g,
57%), 4-Br-Ph (3h, 60%), 4-MeC(O)-Ph (3i, 55%), 4-NC-Ph
(3j, 41%), and 4-phenyl-Ph (3k, 58%) also gave moderate to
good yields. In addition, the desired products could be obtained
in moderate yields even when the substituents bonded to the
meta-position of the benzene ring (4l, 59%; 4m, 54%; 3n, 50%).
The molecular structure of 4l was confirmed by an X-ray
diffraction study.15
b
yield
entry
catalyst (%)
additives (equiv)
(%)
c
1
Pd(OAc)2 (2), Cul (4) NEt3 (5.0), PPh3 (0.04)
Pd(OAc)2 (2), Cul (4) NEt3 (5.0), PPh3 (0.04)
9
2
45
0
3
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Cul (4)
PPh3 (0.04)
4
NEt3 (5.0)
0
5
PPh3 (0.04)
0
6
Cul (4)
NEt3 (5.0)
60
trace
58
59
62
5
7
Cul (4)
none
8
CuCl (4)
CuBr (4)
CuCl2 (4)
CuCl2 (4)
CuCl2 (4)
CuCl2 (4)
CuCl2 (4)
CuCl2 (4)
CuCl2 (4)
Cul (4)
NEt3 (5.0)
9
NEt3 (5.0)
10
11
12
13
NEt3 (5.0)
Cs2CO3 (1.0)
KOH (1.0)
trace
53
88
71
76
83
TMEDA (5.0)
NEt3 (5.0), HC(OEt)3 (5.0)
NEt3 (5.0), MgSO4 (2.0)
NEt3 (5.0), MS (100 mg)
NEt3 (5.0), HC(OEt)3 (5.0)
d
14
15
16
d
17
a
Unless otherwise noted, the reactions were carried out with 0.5 mmol
of 1a in 1.0 mL of dioxane at 120 °C for 12 h. Abbreviations: TMEDA,
N,N,N′,N′-tetramethylethane-1,2-diamine; MS, 4 Å molecular sieves.
b
c
d
Isolated yield. In 1.0 mL of THF at 90 °C for 24 h. Almost the
same results were obtained under N2 or air atmosphere.
under the classical Sonogashira cross-coupling conditions with
the use of 2 mol % of Pd(OAc)2 and 4 mol % of CuI as
catalysts, 4 mol % of PPh3 as ligand, NEt3 as base, and THF as
solvent at 90 °C under N2 atmosphere; unfortunately, the
conversion of 3a was very sluggish even with a prolonged
reaction time (24 h), and the desired 4a was obtained in 9%
yield only (Table 1, entry 1). To our delight, reaction in
dioxane at an elevated temperature (120 °C) gave an increased
yield (45%, entry 2).
In order to figure out which species were catalytic active in
the transformation, we used either Pd(OAc)2 (entries 3 and 4)
or CuI (entries 5 and 6) as catalyst with PPh3 or NEt3 as
additive. It was found that the CuI/NEt3 catalytic system could
catalyze the formation of 4a in good yield (60%), and in the
absence of NEt3, only a trace amount of 4a formed (entry 7).
Other cuprous halides such as CuCl and CuBr, as well as
CuCl2, showed similar catalytic activities in the presence of
Et3N (entries 8−10). Therefore, with the use of CuCl2 as
catalyst, the role of some bases was examined. It was disclosed
that inorganic bases such as Cs2CO3 (entry 11) and KOH
(entry 12) failed to promote the transformation, and TMEDA
was less efficient than NEt3 (entry 13).
When R1 was fluorine atom and R2 was H (3o), Cl (3p), or
MeO (3q), the corresponding chrysene derivatives formed in
moderate yields (entries 15−17). Furthermore, when thienyl-
(3r, entry 18) and naphthyl-substituted (3s, entry 19) were
used, the reactions also occurred to afford chrysene derivatives
in 28% and 67% yield, respectively.
Furthermore, when 2′-(trimethylsilylethynyl)acetophenone
(3t) was used, an unexpected desilicated product 4t was
isolated in 34% yield (eq 1). It was worth noting that the
catalytic system could be applied to synthesize the hetero-
aromatic analogue 4u with a satisfactory yield (64%, eq 2).
However, unfortunately, when an (alkylalkynyl)aceto-
phenone (a favorable substrate in the catalytic system of
PtCl2/CO10) such as 2′-(1-octynyl)acetophenone was either
Inspired by Liu’s work,10 we considered that the formation of
4a might occur via a hydrolysis/dehydration mechanism with
diketone 5a as intermediate (Scheme 2), although the reactivity
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Article
a
with diphenylacetylene (6a) was investigated (eq 3). It was
found that the cross-adduct product 7a did not form at all, and
Table 2. Study of Substrate Scope
b
entry
substrate
R1 = H, R2 = Ph
yield (%)
4a
1
3a
3b
3c
3d
3e
3f
88
42
39
62
70
53
57
60
55
41
58
59
54
50
51
62
45
28
67
2
R1 = H, R2 = 4-MeC6H4
R1 = H, R2 = 4-n-PrC6H4
R1 = H, R2 = 4-t-BuC6H4
R1 = H, R2 = 4-MeOC6H4
R1 = H, R2 = 4-FC6H4
R1 = H, R2 = 4-ClC6H4
R1 = H, R2 = 4-BrC6H4
R1 = H, R2 = 4-MeC(O)C6H4
R1 = H, R2 = 4-NCC6H4
R1 = H, R2 = 4-PhC6H4
R1 = H, R2 = 3-MeC6H4
R1 = H, R2 = 3-MeOC6H4
R1 = H, R2 = 3,4,5-tri-MeOC6H2
R1 = F, R2 = Ph
4b
4c
4d
4e
4f
3
4
5
6
7
3g
3h
3i
4g
4h
4i
8
we can conclude that the dehydration reaction was a crucial and
irreversible step in the formation of 4a as shown in Scheme 3.
9
10
11
12
13
14
15
16
17
18
19
3j
4j
3k
3l
4k
4l
Scheme 3. Proposed Mechanism
3m
3n
3o
3p
3q
3r
3s
4m
4n
4o
4p
4q
4r
R1 = F, R2 = 4-ClC6H4
R1 = F, R2 = 4-MeOC6H4
R1 = H, R2 = thiophene-2-yl
R1 = H, R2 = naphthalen-2-yl
4s
a
Reaction conditions: 3 (0.5 mmol), CuCl2 (4 mol %), NEt3 (5.0
b
equiv), HC(OEt)3 (5.0 equiv), dioxane (1.0 mL), 12 h. Isolated yield.
Therefore, on the basis of previous studies of 2-phenyl-
ethynyl-1-acetylbenzene11,17 and our experimental results, we
propose a plausible mechanism for the formation of chrysene
4a as shown in Scheme 3. First, active intermediate
isobenzopyrylium I is generated reversibly with the aid of
copper salt from 2-phenylethynyl-1-acetylbenzene 3a, and then
intermolecular Diels−Alder reaction occurs between isobenzo-
pyrylium I and 3a to afford intermediate II, which subsequently
undergoes the intramolecular dehydration reaction to give
intermediate III irreversibly, and finally, the transformation of
III occurs to construct the chrysene ring 4a.
subjected to the optimized conditions (indicated in entry 14 of
Table 1) or used in the absence of HC(OEt)3 or in the
presence of water (5.0 equiv), the corresponding chrysene did
not form at all. Instead, in the former case, two products having
the same molecular weight (m/z = 228) as the starting
substrate were determined by GC−MS, and their possible
structures might result from the intramolecular cyclization of
the starting substrate. In the latter case, a considerable amount
of hydrolysis compound (m/z = 246) of the starting substrate
was found in the reaction mixture.16
In addition, as shown in Scheme 2, diketone compound 5a
could not afford the desired chrysene 4a, indicating that the
hydrolysis−dehydration mechanism does not correspond to the
present transformation. In order to gain more information to
understand the mechanism formation of 4, the reaction of 3a
CONCLUSION
■
In conclusion, we have developed an alternative copper-
catalyzed dimerization of 2-alkynyl-1-acetylbenzene to synthe-
size chrysene derivatives, which are promising π-extended
molecules for functional materials. The present procedure
provides a one-pot route to obtain polycyclic aromatic
hydrocarbon from readily available substrates.
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7.52 (t, J = 7.4 Hz, 2H), 7.47−7.35 (m, 2H), 7.28−7.22 (m, 2H),
7.09−7.00 (m, 3H), 6.82 (d, J = 7.9 Hz, 1H), 6.58 (d, J = 7.9 Hz, 1H),
2.89 (s, 3H), 1.21 (s, 9H), 1.18 (s, 9H); 13C NMR (75 MHz, CDCl3)
δ 200.2, 156.3, 150.2, 138.8, 137.7, 136.0, 135.1, 134.5, 133.3, 131.3,
131.1, 130.4, 130.2, 129.5, 129.3, 129.2, 129.0, 127.3, 126.9, 126.3,
126.1, 125.9, 125.5, 125.0, 124.8, 124.6, 124.2, 123.6, 121.7, 35.1, 34.5,
31.4, 31.1, 20.8; HRMS (ESI) calcd for C40H38O [M + H]+ 535.2995,
found 535.2993.
EXPERIMENTAL SECTION
General Methods. All commercial reagents were analytically pure
and used without further purification. Nuclear magnetic resonance
■
1
(NMR) spectra were recorded using CDCl3 as solvent at 298 K. H
NMR (300 MHz) chemical shifts (δ) were referenced to internal
standard TMS (for 1H, δ = 0.00 ppm). 13C NMR (75 and 100 MHz)
chemical shifts were referenced to internal solvent CDCl3 (for 13C, δ =
77.16 ppm). HRMS experiments were performed on a high-resolution
magnetic sector mass spectrometer. The melting points are
uncorrected.
Typical Experimental Procedure for the Synthesis of 3a. A
mixture of 1-(2-bromophenyl)ethanone (1990.4 mg, 10.0 mmol),
Pd(PPh3)2Cl2 (70.1 mg, 0.1 mmol), CuI (38.1 mg, 0.2 mmol), NEt3
(15 mL), phenylacetylene (1630.0 mg, 15 mmol), and THF (15 mL)
was heated at 90 °C (oil bath temperature) with stirring in a 50 mL
screw-capped thick-walled Pyrex tube under N2 atmosphere for 24 h.
After removal of the solvent under reduced pressure, purification was
performed by flash column chromatography on silica gel with
petroleum ether/ethyl acetate (gradient mixture ratio from 100:0 to
98:2) as eluent to afford 2-(phenylethynyl)-1-acetylbenzene (3a) in
82% yield (1804.0 mg).
Typical Experimental Procedure for Synthesis of 4a. A mixture of
2-(phenylethynyl)-1-acetylbenzene (3a, 110.0 mg, 0.5 mmol), CuCl2
(2.7 mg, 0.02 mmol), NEt3 (253.0 mg, 2.5 mmol), HC(OEt)3 (371.0
mg, 2.5 mmol), and dioxane (1.0 mL) was heated at 120 °C (oil bath
temperature) with stirring in a 50 mL screw-capped thick-walled Pyrex
tube under air atmosphere for 12 h. After removal of the solvent under
reduced pressure, purification was performed by flash column
chromatography on silica gel with petroleum ether/ethyl acetate
(gradient mixture ratio from 100:0 to 96:4) as eluent to give 12-
methyl-5-phenyl-6-benzoylchrysene 4a in 88% yield (93.0 mg).
Characterization Data of the Chrysene Derivatives. 12−
Methyl-5-phenyl-6-benzoylchrysene (4a): white solid (88%, 93.0
mg); mp 208−211 °C; 1H NMR (300 MHz, CDCl3) δ 8.90 (d, J = 8.5
Hz, 1H), 8.69 (s, 1H), 8.11 (d, J = 8.2 Hz, 1H), 7.86−7.62 (m, 4H),
7.60−7.31 (m, 6H), 7.20−7.16 (m, 3H), 7.14−7.06 (m, 1H), 6.95 (t, J
= 7.5 Hz, 1H), 6.80 (d, J = 7.5 Hz, 1H), 2.94 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 200.2, 141.7, 138.1, 137.2, 135.0, 134.7, 133.3, 133.0,
131.6, 131.2, 130.5, 130.2, 129.5, 129.4, 129.1, 128.9, 128.3, 128.2,
127.4, 127.4, 127.1, 126.2, 126.1, 126.0, 124.6, 124.3, 123.7, 121.6,
20.8; HRMS (ESI) calcd for C32H22O [M + H]+ 423.1743, found
423.1744.
12-Methyl-5-(4-methoxyphenyl)-6-(4-methoxybenzoyl)chrysene
1
(4e): white solid (70%, 84.6 mg); mp 258−260 °C; H NMR (300
MHz, CDCl3) δ 8.85 (d, J = 8.5 Hz, 1H), 8.66 (s, 1H), 8.14−8.04 (m,
1H), 7.85−7.64 (m, 3H), 7.58−7.41 (m, 5H), 7.10 (m, 1H), 6.95 (dd,
J = 8.4, 2.7 Hz, 1H), 6.73 (dd, J = 8.5, 2.1 Hz, 1H), 6.67 (d, J = 8.9 Hz,
2H), 6.54 (dd, J = 8.5, 2.7 Hz, 1H), 3.77 (s, 3H), 3.75 (s, 3H), 2.92 (s,
3H); 13C NMR (75 MHz, CDCl3) δ 198.6, 163.5, 158.8, 137.6, 134.5,
134.1, 133.4, 132.5, 132.0, 131.5, 131.4, 130.1, 129.5, 129.1, 129.0,
127.2, 126.9, 126.6, 126.2, 125.9, 124.7, 124.2, 123.6, 121.6, 114.5,
113.7, 113.5, 55.5, 55.3, 20.8; HRMS (ESI) calcd for C34H26O3 [M +
H]+ 483.1955, found 483.1955.
12-Methyl-5-(4-fluorophenyl)-6-(4-fluorobenzoyl)chrysene (4f):
1
white solid (53%, 60.8 mg); mp 228−230 °C; H NMR (300 MHz,
CDCl3) δ 8.88 (d, J = 8.5 Hz, 1H), 8.66 (s, 1H), 8.11 (d, J = 8.2 Hz,
1H), 7.82−7.41 (m, 8H), 7.14−7.09 (m, 2H), 6.86 (t, J = 8.6 Hz, 2H),
6.79−6.64 (m, 2H), 2.93 (s, 3H); 13C NMR (75 MHz, CDCl3) δ
198.4, 165.6 (d, J1C−F = 268.5 Hz), 162.29 (d, J1C−F = 260.7 Hz), 137.6
(d, J4
= 3.5 Hz), 137.1, 135.0, 134.5 (d, J4
= 2.7 Hz), 133.9,
= 8.1 Hz), 132.0 (d,
C−F
C−F
133.4, 133.2 (d, J3
= 7.7 Hz), 132.2 (d, J3
C−F
C−F
J3C−F = 9.5 Hz), 131.0, 130.4, 129.6, 128.9, 128.6, 127.5, 127.3, 126.1,
126.0, 125.9, 124.8, 124.4, 123.8, 121.6, 115.8 (d, J2
= 24.8 Hz),
C−F
115.7 (d, J2
= 21.6 Hz), 115.5 (d, J2
= 22.1 Hz), 20.8; HRMS
C−F
C−F
(ESI) calcd for C32H20F2O [M + H]+ 459.1555, found 459.1556.
12-Methyl-5-(4-chlorophenyl)-6-(4-chlorobenzoyl)chrysene (4g):
1
white solid (57%, 70.0 mg); mp 239−240 °C; H NMR (300 MHz,
CDCl3) δ 8.87 (d, J = 8.6 Hz, 1H), 8.65 (s, 1H), 8.11 (d, J = 8.1 Hz,
1H), 7.80−7.65 (m, 3H), 7.63−7.35 (m, 6H), 7.26−7.13 (m, 3H),
6.98 (d, J = 8.0 Hz, 1H), 6.71 (d, J = 7.9 Hz, 1H), 2.93 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 198.6, 140.1, 139.8, 136.8, 136.4, 135.1,
133.7, 133.4, 132.9, 131.8, 130.9, 130.8, 130.4, 129.6, 129.2, 128.9,
128.8, 128.6, 127.6, 127.4, 126.2, 125.9, 125.8, 124.9, 124.4, 123.8,
121.6, 20.8; HRMS (ESI) calcd for C32H20Cl2O [M + H]+ 491.0964,
found 491.0963.
12-Methyl-5-(4-bromophenyl)-6-(4-bromobenzoyl)chrysene (4h):
1
12-Methyl-5-(4-methylphenyl)-6-(4-methylbenzoyl)chrysene
(4b): yellow solid (42%, 47.4 mg); mp 218−220 °C; H NMR (300
white solid (60%, 86.9 mg); mp 262−264 °C; H NMR (300 MHz,
1
CDCl3) δ 8.87 (d, J = 8.5 Hz, 1H), 8.65 (s, 1H), 8.11 (d, J = 8.1 Hz,
1H), 7.80−7.64 (m, 4H), 7.61−7.46 (m, 5H), 7.39−7.27 (m, 5H),
7.19−7.08 (m, 2H), 6.65 (d, J = 8.0 Hz, 1H), 2.93 (s, 3H); 13C NMR
(75 MHz, CDCl3) δ 198.8, 140.6, 136.8, 135.2, 133.7, 133.4, 133.2,
132.2, 132.0, 131. 8, 130.9, 130.4, 129.7, 129.0, 128.7, 128.6, 127.6,
127.5, 126.2, 125.9, 125.8, 125.0, 124.5, 123.8, 123.0, 121.6, 20.8;
HRMS (ESI) calcd for C32H20Br2O [M + H]+ 578.9954, found
578.9953.
MHz, CDCl3) δ 8.87 (d, J = 8.5 Hz, 1H), 8.67 (s, 1H), 8.10 (dd, J =
8.3, 1.0 Hz, 1H), 7.87−7.65 (m, 3H), 7.57−7.41 (m, 5H), 7.26 (s,
1H), 7.15−7.06 (m, 1H), 7.01 (d, J = 8.0 Hz, 2H), 7.00−6.71 (m,
2H), 2.93 (s, 3H), 2.31 (s, 3H), 2.29 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 199.7, 143.9, 138.7, 137.4, 136.9, 135.8, 135.0, 134.5, 133.3,
131.3, 130.1, 129.7, 129.5, 129.5, 129.2, 129.0, 127.2, 126.9, 126.4,
126.1, 125.9, 124.6, 124.2, 123.6, 121.6, 21.8, 21.4, 20.8; HRMS (ESI)
calcd for C34H26O [M + H]+ 451.2056, found 451.2057.
12-Methyl-5-(4-acetylphenyl)-6-(4-acetylbenzoyl)chrysene (4i):
12−Methyl-5-(4-propylphenyl)-6-(4-propylbenzoyl)chrysene (4c):
white solid (39%, 49.5 mg); mp 157−158 °C; H NMR (300 MHz,
1
white solid (55%, 69.7 mg); mp 266−268 °C; H NMR (300 MHz,
1
CDCl3) δ 8.89 (d, J = 8.5 Hz, 1H), 8.67 (s, 1H), 8.11 (d, J = 8.0 Hz,
1H), 8.02 (d, J = 7.3 Hz, 1H), 7.78−7.67 (m, 5H), 7.61−7.46 (m,
7H), 7.10−7.01 (m, 1H), 6.89 (d, J = 7.0 Hz, 1H), 2.93 (s, 3H), 2.55
(s, 3H), 2.52 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 199.2, 197.7,
197.4, 146.7, 140.8, 140.2, 136.5, 135.9, 135.4, 133.9, 133.4, 131.9,
130.7, 130.5, 129.7, 129.5, 129.0, 128.5, 128.3, 127.6, 126.3, 125.9,
125.6, 124.9, 124.5, 123.9, 121.6, 26.9, 26.8, 20.8; HRMS (ESI) calcd
for C36H26O3 [M + H]+ 507.1955, found 507.1951.
CDCl3) δ 8.84 (d, J = 8.5 Hz, 1H), 8.64 (s, 1 H), 8.05 (d, J = 8.1 Hz,
1H), 7.78 (dd, J = 8.1, 5.7 Hz, 2H), 7.67 (t, J = 7.6 Hz, 1H), 7.51 (t, J
= 7.5 Hz, 2H), 7.44 (t, J = 7.5 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.18
(d, J = 7.5 Hz, 1H), 7.02 (t, J = 7.7 Hz, 1H), 6.90 (d, J = 8.1 Hz, 2H),
6.70−6.61 (m, 2H). 2.89 (s, 3H), 2.49 (t, J = 7.6 Hz, 2H), 2.47 (t, J =
7.6 Hz, 2H), 1.53−1.48 (m, 4H), 0.82 (t, J = 7.1 Hz, 3H), 0.80 (t, J =
7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 200.0, 148.3, 141.6, 139.0,
137.4, 136.1, 135.0, 134.5, 133.3, 131.3, 130.4, 130.1, 129.6, 129.5,
129.3, 129.0, 128.5, 128.2, 127.2, 126.9, 126.3, 126.1, 125.9, 124.5,
124.2, 123.6, 121.6, 38.0, 37.6, 24.4, 24.1, 20.8, 13.7, 13.4; HRMS
(ESI) calcd for C40H38O [M + H]+ 535.29954, found 535.29926;
HRMS (ESI) calcd for C38H34O [M + H]+ 507.2682, found 507.2687.
12−Methyl-5-(4-tert-butylphenyl)-6-(4-tert-butylbenzoyl)-
chrysene (4d): white solid (62%, 78.6 mg); mp 206−208 °C; 1H
NMR (300 MHz, CDCl3) δ 8.85 (d, J = 8.5 Hz, 1H), 8.65 (s, 1H),
8.05 (d, J = 8.2 Hz, 1H), 7.90−7.79 (m, 2H), 7.68 (t, J = 7.6 Hz, 1H),
12-Methyl-5-(4-cyanophenyl)-6-(4-cyanobenzoyl)chrysene (4j):
white solid (41%, 48.5 mg); mp >300 °C; 1H NMR (300 MHz,
CDCl3) δ 8.89 (d, J = 8.5 Hz, 1H), 8.64 (s, 1H), 8.12 (d, J = 8.2 Hz,
1H), 7.83−7.65 (m, 4H), 7.62−7.44 (m, 7H), 7.25 (d, J = 8.4 Hz,
1H), 7.10 (t, J = 7.8 Hz, 1H), 6.84 (d, J = 6.1 Hz, 1H), 2.93 (s, 3H);
13C NMR (75 MHz, CDCl3) δ 198.2, 146.5, 140.4, 135.9, 135.8, 133.4,
133.2, 132.8, 132.4, 132.0, 131.3, 130.7, 130.2, 129.7, 129.4, 128.7,
128.1, 128.0, 127.9, 126.5, 125.7, 125.1, 124.7, 124.0, 121.5, 118.5,
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Article
117.7, 116.6, 111.5, 20.8; HRMS (ESI) calcd for C34H20N2O [M +
H]+ 473.1648, found 473.1646.
136.2 (d, J4
= 4.1 Hz), 136.0, 135.4, 135.0, 134.4, 132.8, 132.7,
C−F
132.5, 131.5, 131.1, 130.7, 130.0, 130.0 (d, J3
= 9.3 Hz), 129.5,
C−F
129.0 (d, J3C−F = 10.5 Hz), 128.9, 126.6 (d, J3C−F = 9.2 Hz), 126.6 (d,
J3C−F = 8.8 Hz), 124.7 (d, J4C−F = 4.1 Hz), 120.9, 117.1 (d, J2C−F = 24.3
Hz), 115.5 (d, J2C−F = 23.8 Hz), 113.7 (d, J2C−F = 25.0 Hz), 110.2 (d,
12-Methyl-5-(4-phenylphenyl)-6-(4-phenylbenzoyl)chrysene (4k):
1
white solid (58%, 83.4 mg); mp 298−300 °C; H NMR (300 MHz,
CDCl3) δ 8.78 (d, J = 8.5 Hz, 1H), 8.57 (s, 1H), 7.98 (d, J = 8.2 Hz,
1H), 7.78−7.70 (m, 2H), 7.63−7.55 (m, 3H), 7.49−7.18 (m, 17H),
7.11−7.04 (m, 1H), 6.96 (t, J = 7.8 Hz, 1H), 6.76 (d, J = 7.9 Hz, 1H),
2.81 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 199.7, 145.6, 140.8,
140.6, 139.9, 137.4, 137.1, 134.8, 134.7, 133.4, 132.0, 131.2, 131.0,
130.3, 130.1, 129.6, 129.2, 128.9, 128.8, 128.2, 127.5, 127.4, 127.3,
127.2, 127.1, 127.0, 126.8, 126.2, 126.1, 124.8, 124.3, 123.7, 121.7,
20.8; HRMS (ESI) calcd for C44H30O1 [M + H]+ 575.2369, found
575.2369.
J2
= 22.0 Hz), 21.0; HRMS (ESI) calcd for C32H18Cl2F2O [M +
C−F
H]+ 527.0776, found 527.0775.
3,8-Difluoro-12-methyl-5-(4-methoxyphenyl)-6-(4-methoxy-
benzoyl)chrysene (4q): white solid (45%, 58.4 mg); mp 285−288 °C;
1H NMR (300 MHz, CDCl3) δ 8.81 (m, 1H), 8.50 (s, 1H), 8.04 (m,
1H), 7.52−7.41 (m, 3H), 7.39−7.32 (m, 2H), 7.31−7.25 (m, 1H),
7.24−7.17 (m, 1H), 6.96 (m, 1H), 6.76−6.65 (m, 3H), 6.57 (m, 1H),
3.77 (s, 3H), 3.76 (s, 3H), 2.88 (s, 3H); 13C NMR (100 MHz, CDCl3)
12-Methyl-5-(3-methylphenyl)-6-(3-methylbenzoyl)chrysene (4l,
a mixture of atropisomers): white solid (59%, 66.5 mg); mp 177−
180 °C; 1H NMR (300 MHz, CDCl3) δ 8.91 (d, J = 8.5 Hz, 1H), 8.71
(s, 1H), 8.12 (d, J = 8.2 Hz, 1H), 7.95−7.81 (m, 2H), 7.73 (t, J = 7.6
Hz, 1H), 7.62−7.54 (m, 1H), 7.53−7.45 (m, 2H), 7.36−7.07 (m, 5H),
7.02 (d, J = 7.1 Hz, 1H), 6.90 (t, J = 7.5 Hz, 1H), 6.68 (m, 1H), 2.94
(s, 3H), 2.43 (s, 1.5H), 2.23 (s, 3H), 1.96 (s, 1.5H); 13C NMR (75
MHz, CDCl3) δ 200.3, 141.7, 138.4, 137.8, 137.7, 137.5, 137.3, 135.1,
134.6, 133.7, 133.6, 133.3, 132.1, 131.3, 131.2, 130.2, 129.7, 129.7,
129.5, 129.2, 129.0, 128.7, 128.6, 128.1, 128.0, 127.4, 127.2, 126.9,
126.8, 126.1, 125.9, 124.7, 124.2, 123.6, 121.6, 21.6, 21.2, 21.0, 20.8;
HRMS (ESI) calcd for C34H26O [M + H]+ 451.2056, found 451.2056.
12-Methyl-5-(3-methoxyphenyl)-6-(3-methoxybenzoyl)chrysene
(4m, a mixture of atropisomers): white solid (54%, 65.2 mg); mp
156−158 °C; 1H NMR (300 MHz, CDCl3) δ 8.89 (d, J = 8.5 Hz, 1H),
8.69 (s, 1H), 8.11 (d, J = 8.2 Hz, 1H), 7.89−7.80 (m, 2H), 7.72 (t, J =
7.7 Hz, 1H), 7.61−7.46 (m, 2H), 7.35 (t, J = 7.8 Hz, 1H), 7.25−7.02
(m, 5H), 7.00−6.89 (m, 1H), 6.79 (t, J = 8.1 Hz, 1H), 6.51−6.41 (m,
1H), 3.86 (s, 1.5H), 3.72 (s, 3H), 3.34 (s, 1.5H), 2.93 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 199.9, 199.8, 159.9, 159.5, 142.9, 140.0,
139.6, 137.1, 134.8, 134.7, 133.2, 131.1, 130.2, 130.0, 129.6, 129.4,
129.2, 129.0, 128.8, 127.3, 127.1, 126.0, 124.8, 124.7, 124.2, 123.6,
123.1, 122.8, 121.6, 119.6, 116.7, 115.0, 114.5, 113.7, 113.0, 112.9,
55.4, 55.0, 20.7; HRMS (ESI) calcd for C34H26O3 [M + H]+ 483.1955,
found 483.1951.
δ 197.8, 163.7, 161.7 (d, J1
= 248.2 Hz), 159.8 (d, J1
= 243.5
C−F
C−F
Hz), 159.3, 137.0 (d, J4
= 4.4 Hz), 135.8, 134.8, 132.9, 132.9 (d,
C−F
J3C−F = 9.5 Hz), 132.3, 132.0, 131.3, 131.0, 130.8, 130.4 (d, J3C−F = 8.9
Hz), 130.0, 126.33 (d, J3
= 8.9 Hz), 126.31 (d, J3
= 9.0 Hz),
C−F
C−F
125.4 (d, J4 = 4.7 Hz), 120.89, 120.87, 116.5 (d, J2
= 24.1 Hz),
= 26.7 Hz),
C−F
2
C−F
115.2 (d, J2
= 24.1 Hz), 114.8, 114.0, 113.9 (d, J
C−F
113.6, 110.3 (d, J 2C−F = 21.7 Hz), 55.5, 55.4, 20.9; HRMS (ESI) calcd
for C34H24F2O3 [M + H]+ 519.1766, found 519.1768.
12-Methyl-5-(thiophene-2-yl)-6-(thiophene-2-carbonyl)chrysene
(4r): yellow solid (28%, 30.5 mg); mp 212−214 °C; H NMR (300
1
MHz, CDCl3) δ 8.82 (d, J = 8.6 Hz, 1H), 8.60 (s, 1H), 8.09 (dd, J =
8.3, 1.1 Hz, 1H), 7.94 (d, J = 8.7 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H),
7.71 (m, 1H), 7.58−7.50 (m, 3H), 7.26 (d, J = 5.0 Hz, 1H), 7.22−7.15
(m, 2H), 6.98 (m, 2H), 6.85−6.80 (m, 1H), 2.91 (s, 3H); 13C NMR
(75 MHz, CDCl3) δ 191.5, 143.1, 138.4, 135.4, 135.2, 134.8, 133.3,
131.1, 130.2, 130.0, 128.6, 128.4, 128.0, 127.9, 127.5, 127.5, 127.3,
127.2, 126.8, 126.3, 126.3, 124.9, 124.2, 123.7, 121.4, 20.8; HRMS
(ESI) calcd for C28H18S2O [M + H]+ 435.0872, found 435.0871.
12-Methyl-5-(naphthalen-2-yl)-6-(naphthalene-2-carbonyl)-
chrysene (4s): white solid (67%, 87.6 mg); mp 215−217 °C; 1H NMR
(300 MHz, CDCl3) δ 8.91 (d, J = 8.5 Hz, 1H), 8.72 (s, 1H), 8.21−
8.05 (m, 2H), 7.90 (m, 8.1 Hz, 2H), 7.74 (m, 4H), 7.67−7.59 (m,
2H), 7.56−7.45 (m, 5H), 7.45−7.37 (m, 3H), 7.32−7.25 (m, 1H),
7.20−7.04 (m, 1H), 6.94−6.83 (m, 1H), 2.94 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 200.0, 139.4, 137.8, 136.2, 135.5, 135.4, 134.9, 133.5,
133.3, 132.4, 132.2, 132.1, 131.5, 131.3, 130.7, 130.4, 129.7, 129.5,
129.4, 129.2, 128.8, 128.6, 128.5, 128.3, 128.0, 127.8, 127.7, 127.5,
127.4, 127.3, 126.6, 126.3, 126.1, 124.9, 124.5, 124.2, 124.2, 123.7,
121.7, 20.9; HRMS (ESI) calcd for C40H26O [M + H]+ 523.2056,
found 523.2054.
12-Methyl-5-(3,4,5-trimethoxyphenyl)-6-(3,4,5-trimethoxy-
benzoyl)chrysene (4n): white solid (50%, 75.4 mg); mp 196−198 °C;
1H NMR (300 MHz, CDCl3) δ 8.88 (d, J = 8.5 Hz, 1H), 8.68 (s, 1H),
8.10 (d, J = 8.2 Hz, 1H), 7.90 (d, J = 8.7 Hz, 1H), 7.80 (d, J = 8.2 Hz,
1H), 7.76−7.68 (m, 1H), 7.62−7.46 (m, 2H), 7.17 (t, J = 7.8 Hz, 1H),
6.85 (s, 2H), 6.78 (s, 1H), 6.09 (s, 1H), 3.84 (s, 6H), 3.82 (s, 3H),
3.66 (s, 6H), 3.29 (s, 3H), 2.93 (s, 32H); 13C NMR (75 MHz, CDCl3)
δ 199.0, 153.6, 153.2, 152., 142.8, 137.5, 137.1, 137., 134.9, 134.9,
134.0, 133.2, 131.1, 130.2, 129.6, 129.0, 127.4, 127.2, 126.2, 126.0,
125.8, 125.0, 124.2, 123.7, 121.6, 109.2, 108.0, 107.2, 61.1, 60.9, 56.4,
56.3, 55.8, 20.8; HRMS (ESI) calcd for C38H34O7 [M + H]+ 603.2377,
found 603.2376.
3,8-Difluoro-12-methyl-5-phenyl-6-benzoylchrysene (4o): white
solid (51%, 58.5 mg); mp 236−238 °C; 1H NMR (300 MHz, CDCl3)
δ 8.75 (m, 1H), 8.42 (s, 1H), 7.95 (m, 1H), 7.52 (d, J = 7.0 Hz, 1H),
7.43−7.27 (m, 6H), 7.13 (m, 5H), 6.89 (t, J = 7.2 Hz, 1H), 6.69 (d, J =
7.3 Hz, 1H), 2.80 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 199.4, δ
12-Methyl-6-formylchrysene (2t): white solid (34%, 23.4 mg); mp
223−225 °C; H NMR (300 MHz, CDCl3) δ 10.40 (s, 1H), 9.41−
1
9.34 (m, 1H), 8.93 (s, 1H), 8.74−8.64 (m, 2H), 8.35 (s, 1H), 8.12−
8.07 (m, 1H), 7.79−7.66 (m, 4H), 2.82 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 193.7, 137.8, 134.3, 131.9, 130.7, 130.6, 129.4, 128.9, 128.4,
127.5, 127.5, 127.1, 125.7, 125.6, 125.0, 123.3, 123.2, 121.4, 21.0;
HRMS (ESI) calcd for C20H14O [M + H]+ 271.1117, found 271.1117.
(4-Methoxyphenyl)(9-(4-methoxyphenyl)-5-methylnaphtho[1,2-
b:6,5-b′]dithiophene-10-yl)methanone (4u): yellow solid (64%, 79.2
1
mg); mp 248−250 °C; H NMR (300 MHz, CDCl3) δ 7.96 (s, 1H),
161.8 (d, J1C−F= 248.33 Hz), 159.8 (d, J1
= 243.73 Hz), 140.6,
7.60 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 5.4 Hz, 1H), 7.20 (d, J = 5.7 Hz,
2H), 7.12 (d, J = 5.4 Hz, 2H), 6.82 (d, J = 4.4 Hz, 2H), 6.74 (d, J = 8.9
Hz, 3H), 6.34 (d, J = 5.6 Hz, 1H), 3.80 (s, 3H), 3.78 (s, 3H), 2.76 (s,
3H); 13C NMR (75 MHz, CDCl3) δ 197.0, 163.7, 159.2, 141.3, 138.1,
136.3, 134.2, 133.6, 133.0, 132.2, 132.1, 131.2, 128.2, 126.9, 126.0,
124.7, 124.4, 123.9, 120.7, 114.0, 113.6, 55.5, 55.3, 20.9; HRMS (ESI)
calcd for C30H22S2O3 [M + H]+ 495.1083, found 495.1084.
C−F
137.9, 136.5 (d, J4
= 4.2 Hz), 135.0, 133.3, 132.7 (d, J3
= 9.4
C−F
C−F
Hz), 131.3, 130.9, 130.3, 130.2 (d, J3C−F = 9.3 Hz), 130.0, 129.4, 129.2,
128.6, 128.3, 128.0, 126.4 (d, J3C−F = 8.62 Hz), 126.3 (d, J3C−F = 9.07
Hz), 125.0 (d, J4C−F = 3.3 Hz), 120.9, 116.7 (d, J2C−F = 24.0 Hz), 115.2
(d, J2C−F = 24.0 Hz), 113.9 (d, J2C−F = 25.3 Hz), 110.2 (d, J2C−F = 21.9
Hz), 20.9; HRMS (ESI) calcd for C32H20F2O [M + H]+ 459.1555,
found 459.1555.
3,8-Difluoro-12-methyl-5-(4-chlorophenyl)-6-(4-chlorobenzoyl)-
1
ASSOCIATED CONTENT
chrysene (4p): white solid (62%, 81.7 mg); mp >300 °C; H NMR
■
(300 MHz, CDCl3) δ 8.84 (m, 1H), 8.51 (s, 1H), 8.07 (m, 1H), 7.54−
7.42 (m, 2H), 7.38 (m, 1H), 7.36−7.32 (m, 2H), 7.29 (m, 1H), 7.26−
7.21 (m, 2H), 7.21−7.16 (m, 2H), 7.01 (d, J = 7.7 Hz, 1H), 6.69 (d, J
= 7.8 Hz, 1H), 2.90 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 197.9,
161.9 (d, J1C−F = 249.3 Hz), 159.9 (d, J1C−F = 244.7 Hz), 140.1, 139.0,
S
* Supporting Information
1
Copies of H and 13C NMR spectra of all products and X-ray
structural details of 4l. This material is available free of charge
via the Internet at http://pubs.acs.org.
4356
dx.doi.org/10.1021/jo500182k | J. Org. Chem. 2014, 79, 4352−4357

The Journal of Organic Chemistry
Article
(13) (a) Mio, M. J.; Kopel, L. C.; Braun, J. B.; Gadzikwa, T. L.; Hull,
K. L.; Brisbois, R. G.; Markworth, C. J.; Grieco, P. A. Org. Lett. 2002, 4,
3199. (b) Negishi, E.-I.; Anastasia, L. Chem. Rev. 2003, 103, 1979.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: ruimao@mail.tsinghua.edu.cn.
́
(c) Chinchilla, R.; Najera, C. Chem. Rev. 2007, 107, 874.
(14) For recent work, see: (a) Huang, Q.; Hua, R. Chem.Eur. J.
2009, 15, 3817. (b) Wu, B.; Hua, R. Tetrahedron Lett. 2010, 51, 6433.
(c) Su, J.; Ju, J.; Hua, R. Curr. Org. Synth. 2012, 9, 273. (d) Zheng, L.;
Ju, J.; Bin, Y.; Hua, R. J. Org. Chem. 2012, 77, 5794. (e) Zheng, L.;
Hua, R. Chem.Eur. J. 2013, 20, 2352.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(15) The detailed X-ray diffraction data of 4l are reported in the
Supporting Information.
This project was supported by the National Natural Science
Foundation of China (21032004, 20972084).
(16) The reaction and results of (alkylalkynyl)acetophenones under
the optimized reaction conditions were reported in our original
manuscript. On the basis of one reviewer’s comments, the reaction was
repeated in the absence of dehydrating agent or in the presence of
water, and no corresponding chrysenes formed at all. As required by
the reviewer, the reactions of (arylalkynyl)acetophenone of 3a using
PtCl2/CO catalytic system reported by Liu’s group10 were also
examined in the presence of water or absence of water, and both of the
reactions did not afford 4a. In the absence of water, the reaction gave a
considerable amount of product having a molecular weight the same as
that of the starting material (m/z = 220), possibly due to the
intramolecular cyclization reaction. In the presence of water, the
reaction produced a considerable amount of hydrolysis compound (m/
z = 246) as confirmed by GC−MS.
REFERENCES
■
(1) For selected reviews of polycyclic aromatic hydrocarbons; see:
(a) Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36,
1902. (b) Coropceamu, V.; Cornil, J.; Da Silva Filho, D. A.; Olivier, Y.;
Silbey, R.; Bredas, J. L. Chem. Rev. 2007, 107, 926. (c) Dong, H.; Zhu,
H.; Meng, Q.; Gong, X.; Hu, W. Chem. Soc. Rev. 2012, 41, 1754.
(d) Keyte, I. J.; Harrisonz, R. M.; Lammel, G. Chem. Soc. Rev. 2013, 42,
9333.
(2) (a) Atklnson, G. H.; Gllmore, D. A.; Dosser, L. R.; Palllx, J. B. J.
Phys. Chem. 1982, 86, 2305. (b) Cai, X.; Hara, M.; Kawai, K.; Tojo, S.;
Majima, T. Chem. Phys. Lett. 2003, 368, 365. (c) Wang, C.; Dong, H.;
Hu, W.; Liu, Y.; Zhu, D. Chem. Rev. 2012, 112, 2208.
(3) Little, M.; Lan, H.; Raftery, J.; Morrison, J. J.; McDouall, J. J. W.;
Yeates, S. G.; Quayle, P. Eur. J. Org. Chem. 2013, 6038.
(4) (a) Okamoto, H.; Kawasaki, N.; Kaji, Y.; Kubozono, Y.; Fujiwara,
A.; Yamaji, M. J. Am. Chem. Soc. 2008, 130, 10470. (b) Kunugi, Y.;
Ikari, M.; Okamoto, K. ECS Trans. 2010, 25, 11. (c) Shinamura, S.;
Osaka, I.; Miyazaki, E.; Nakao, A.; Yamagishi, M.; Takeya, J.; Takimiya,
K. J. Am. Chem. Soc. 2011, 133, 5024. (d) Kunugi, Y.; Arai, T.;
Kobayashi, N.; Otsuki, H.; Nishinaga, T.; Okamoto, K. J. Photopolym.
Sci. Technol. 2011, 24, 345.
(17) (a) Tovar, R.; Swager, T. M. J. Org. Chem. 1999, 64, 6499.
(b) Dyker, G.; Hildebrandt, D.; Liu, J.; Merz, K. Angew. Chem., Int. Ed.
2003, 42, 4399.
(5) Ionkin, A. S.; Marshall, W. J.; Fish, B. M.; Bryman, L. M.; Wang,
Y. Chem. Commun. 2008, 2319.
(6) Wu, T.-L.; Chou, H.-H.; Huang, P.-Y.; Cheng, C.-H.; Liu, R.-S. J.
Org. Chem. 2014, 79, 267.
(7) For selected examples of chrysene syntheses; see: (a) Leznoff, C.
C.; Hayward, R. J. Can. J. Chem. 1972, 50, 528. (b) Nagel, D. L.;
Kupper, R.; Antonson, K.; Wallcave, L. J. Org. Chem. 1977, 42, 3626.
(c) Lyle, T. A.; Daub, G. H. J. Org. Chem. 1979, 44, 4933.
(d) LeHoullier, C. S.; Gribble, G. W. J. Org. Chem. 1983, 48, 1682.
(e) Hwang, K.-J.; O’Neil, J. P.; Katzenellenbogen, J. A. J. Org. Chem.
1992, 57, 1262. (f) Hamza, K.; Abu-Reziq, R.; Avnir, D.; Blum, J. Org.
Lett. 2004, 6, 925. (g) Shen, H.-C.; Tang, J.-M.; Chang, H.-K.; Yang,
C.-W.; Liu, R.-S. J. Org. Chem. 2005, 70, 10113. (h) Isobe, H.;
Hitosugi, S.; Matsuno, T.; Iwamoto, T.; Ichikawa, J. Org. Lett. 2009,
11, 4026. (i) Okamoto, H.; Yamaji, M.; Gohda, S.; Kubozono, Y.;
Komura, N.; Sato, K.; Sugino, H.; Satake, K. Org. Lett. 2011, 13, 2758.
(8) (a) Korobka, I. V.; Kuznetsov, E. V. Khim. Geterotsikl. Soedin.
1982, 1184. (b) Korobka, I. V.; Voloshina, A. I.; Kuznetsov, E. V.
Khim. Geterotsikl. Soedin. 1984, 1472. (c) Korobka, I. V.; Revinskii, Yu.
V.; Kuznetsov, E. V. Khim.Geterotsikl. Soedin. 1985, 910.
(9) Kuznetsov, E. V.; Shcherbakova, I. V.; Balaban, A. T. Adv.
Heterocycl. Chem. 1990, 50, 157.
(10) Das, A.; Liao, H.-H.; Liu, R.-S. J. Org. Chem. 2007, 72, 9214.
(11) (a) Asao, N.; Takahashi, K.; Lee, S.; Kasahara, T.; Yamamoto, Y.
J. Am. Chem. Soc. 2002, 124, 12650. (b) Asao, N.; Kasahara, T.;
Yamamoto, Y. Angew. Chem., Int. Ed. 2003, 42, 3504. (c) Liu, L.-P.;
Hammond, G. B. Org. Lett. 2010, 12, 4640.
(12) (a) Barluenga, J.; Vaz
M. J. Am. Chem. Soc. 2003, 125, 9028. (b) Yue, D.; Ca,
́
quez-Villa, H.; Ballesteros, A.; Gonzal
́
ez, J.
́
N. D.; Larock,
R. C. J. Org. Chem. 2006, 71, 3381. (c) Yeom, H.-S.; Lee, L.; Lee, J.-E.;
Shin, S. Org. Biomol. Chem. 2009, 7, 4744. (d) Chernyak, N.; Gorelsky,
S. I.; Gevorgyan, V. Angew. Chem., Int. Ed. 2011, 50, 2342. (e) Zheng,
D.; Li, S.; Wu, J. Org. Lett. 2012, 14, 2655. (f) Yu, S.-Y.; Zhang, H.;
Gao, Y.; Mo, L.; Wang, S.; Yao, Z.-J. J. Am. Chem. Soc. 2013, 135,
11402.
4357
dx.doi.org/10.1021/jo500182k | J. Org. Chem. 2014, 79, 4352−4357