Synthesis of arylated anthraquinones by site-selective Suzuki-Miyaura reactions of the bis(triflates) of 1,3-di(hydroxy)anthraquinones

Article abstract of DOI:10.1016/j.tet.2013.08.041

Arylated anthraquinones were prepared by Suzuki-Miyaura reactions of the bis(triflates) of various 1,3-(dihydroxy)anthraquinones. While the reactions of the bis(triflates) of parent 1,3-(dihydroxy)anthraquinone and of 2-chloro-1,3-di(hydroxy)anthraquinone proceeded with very good site-selectivity, the corresponding reactions of the bis(triflate) of 2-fluoro-1,3- diarylanthraquinones were not site-selective, which was explained based on the π-donating effect of the fluorine atom.

Full text of DOI:10.1016/j.tet.2013.08.041

Tetrahedron 69 (2013) 9013e9024
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of arylated anthraquinones by site-selective
SuzukieMiyaura reactions of the bis(triflates) of 1,3-di(hydroxy)
anthraquinones
,
b
c
a
Omer A. Akrawi a, Afsar Khan a , Tamas Patonay , Alexander Villinger ,
ꢀ
,d,
Peter Langer a
*
a
€
€
Institut fur Chemie, Universitat Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
b Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Postal Code 22060, Pakistan
c
ꢀ
Department of Organic Chemistry, University of Debrecen, Egyetem ter 1, H-4032 Debrecen, Hungary
Leibniz-Institut fur Katalyse an der Universitat Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
d
€
€
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 June 2013
Received in revised form 8 August 2013
Accepted 16 August 2013
Available online 23 August 2013
Arylated anthraquinones were prepared by SuzukieMiyaura reactions of the bis(triflates) of various 1,3-
(dihydroxy)anthraquinones. While the reactions of the bis(triflates) of parent 1,3-(dihydroxy)anthra-
quinone and of 2-chloro-1,3-di(hydroxy)anthraquinone proceeded with very good site-selectivity, the
corresponding reactions of the bis(triflate) of 2-fluoro-1,3-diarylanthraquinones were not site-selective,
which was explained based on the
p
-donating effect of the fluorine atom.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Anthraquinones
Catalysis
Palladium
Regioselectivity
1. Introduction
Because of the importance of anthraquinones for many medi-
cally18 and industrially relevant applications,19 several synthetic
methods have been developed for their preparation. The Frie-
deleCrafts acylation reaction of phthalic anhydrides or phthaloyl
chlorides with substituted benzene derivatives is the most com-
mon synthetic method used for the synthesis of anthraquinones.20
Hauser annulations have also been successfully used for preparing
the anthraquinone core, which rely on the reaction of p-benzo-
quinones as acceptors and phthalides as donors.21 Anthraquinones
have been prepared also based on the DielseAlder by reaction of
Brassard’s dienes with naphthaquinones.22 In addition, transition
metal catalyzed reactions represent powerful tools for the syn-
thesis of arylated anthraquinones. For example, the catalytic
[2þ2þ2] cyclotrimerization of 1,2-bis(arylpropionyl)benzenes with
various monoalkynes in the presence of Ru(I) or Ru(II) result in the
formation of arylated anthraquinones.23 Stille24 and Suzu-
kieMiyaura25 reactions were also successfully used for the syn-
thesis of arylated anthraquinones.
Anthraquinones are an important class of natural compounds
with widespread distribution in plants, such as herbs, which are
used for the treatment of many diseases.1e3 For example, Rumex
japonicus Houtt., a rich source of anthraquinones, is used for the
treatment of heat phlegm, jaundice, constipation, scabies and
uterine haemorrhage.4 Chloroemodin, chrysophanol, danthron,
rhein and physcion are biologically active anthraquinones and they
constitute a major component of Rhubarb, which is one of the most
famous and ancient herb medicines. Halogenated anthraquinones
have recently been isolated from the marine-derived fungus
Aspergillus sp. SCSIO F063, which shows cytotoxic activities against
human breast adenocarcinoma, human glioblastoma and human
lung carcinoma (Fig. 1).5 Synthetic and natural anthraquinones
have also been reported as anti-inflammatory,6 anti-bacterial,7
hepatoprotective,8 anti-angiogenic activity,9 anti-fungal,10 anti-
cancer,11 antidiabetic,12 anti-oxidant,13 anti-allergic14 and anti-
filarial agents.15 Synthetic anthraquinones have also been used as
chemical sensors,16 and as stabilizers of light-modulating fluids.17
Recently, we have reported site-selective SuzukieMiyaura re-
actions of the bis(triflate) of 1,2-di(hydroxy)anthraquinone and of
the tris(triflate) of 1,2,4-tri(hydroxy)anthraquinone.26 The selec-
tivity is controlled by electronic parameters and the first attack
occurred at the sterically more hindered, electronically more
* Corresponding author. E-mail address: peter.langer@uni-rostock.de (P. Langer).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.08.041

9014
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
Fig. 1. Biologically active and naturally occurring anthraquinones.
deficient position next to the carbonyl group. In 2011, we reported
preliminary results related to SuzukieMiyaura reactions of the
bis(triflate) of 1,3-di(hydroxy)anthraquinone.27 Herein, we report
full details of this study and an extension of the preparative scope
to the bis(triflates) of 2-chloro- and 2-fluoro-1,3-di(hydroxy)an-
thraquinone. In this context, we also report a convenient synthesis
of the starting materials based on [4þ2] cycloaddition reactions of
chlorinated and fluorinated 1,3-bis(silyloxy)-1,3-butadienes.
(Scheme 2, Table 2). Very good yields were obtained when Pd(PPh3)4
and K3PO4 were employed as the catalyst and base, respectively. The
reactions of arylboronic acids containing electron donating and
electron withdrawing substituents proceeded in equally good yields.
The structure of 6a was independently confirmed by X-ray crystal
structure analysis (Fig. 2).28
2. Results and discussion
1,3-Di(hydroxy)anthraquinones 3aec were prepared in 57e70%
yields by [4þ2] cycloaddition of 1,3-bis(silyloxy)-1,3-butadienes
2aec with 2-bromonaphthoquinone (1) (Scheme 1, Table 1). The
products were transformed into their bis(triflates) in good yields.
The SuzukieMiyaura reaction of 4aec with arylboronic acids 5aej
(2.2e2.4 equiv) afforded the 1,3-diarylanthraquinones, 2-chloro-1,3-
diarylanthraquinones and 2-fluoro-1,3-diarylanthraquinones 6aeq
Scheme 2. Synthesis of 6aeq. Conditions: i, for 6aeh: 4a (1.0 equiv), ArB(OH)2
(2.2 equiv), Pd(PPh3)4 (5 mol %), K3PO4 (3.0 equiv), dioxane, 100 ꢀC, 7 h; for 6iel: 4b
(1.0 equiv), ArB(OH)2 (2.4 equiv), Pd(PPh3)4 (7 mol %), K3PO4 (3.0 equiv), dioxane,
115 ꢀC, 10 h; for 6meq: 4c (1.0 equiv), ArB(OH)2 (2.2 equiv), Pd(PPh3)4 (6 mol %), K3PO4
(3.0 equiv), dioxane, 110 ꢀC, 8 h.
Scheme 1. Synthesis of 4aec: conditions: i, 1 (1.0 equiv), 2aec (1.5 equiv), 20 ꢀC, 12 h; ii, H2O; synthesis of 4aec; iii, 3aec (1.0 equiv), Tf2O (2.4 equiv), pyridine (4.0 equiv), CH2Cl2,
20 ꢀC, 8 h.
Table 1
Synthesis of 3aec and 4aec
The reaction of bis(triflates) 4a,b with arylboronic acids
5a,f,gei,kem
(1.0
equiv)
afforded
the
3-aryl-1-(tri-
2e4
X
% (3)a
% (4)a
fluoromethylsulfonyloxy)anthraquinones 7aek in 71e90% yield
(Scheme 3, Table 3). Very good yields were again obtained when
the reactions were carried out using Pd(PPh3)4 (3 mol %) as the
catalyst, K3PO4 (1.5 equiv) as the base and dioxane as the solvent.
Both electron rich and electron poor arylboronic acids could be
a
b
c
H
Cl
F
57
61
70
78
70
85
a
Yields of isolated compound.

O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
9015
Table 2
Table 3
Synthesis of 6aeq
Synthesis of 7aek
5
6
X
Ar
% (6)a
5
7
X
Ar
% (7)a
a
b
c
d
e
f
g
h
c
f
g
h
b
c
g
i
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
H
H
H
H
H
H
H
H
Cl
Cl
Cl
Cl
F
4-(MeO)C6H4
4-EtC6H4
4-MeC6H4
4-tBuC6H4
3-MeC6H4
3,5-Me2C6H3
4-ClC6H4
4-FC6H4
4-MeC6H4
3,5-Me2C6H3
4-ClC6H4
4-FC6H4
4-EtC6H4
4-MeC6H4
4-ClC6H4
3-ClC6H4
C6H5
76
88
80
75
71
82
84
78
85
77
71
75
90
88
76
81
82
a
f
g
h
k
i
a
f
g
l
a
b
c
d
e
f
g
h
i
H
H
H
H
H
H
Cl
Cl
Cl
Cl
Cl
4-(MeO)C6H4
3,5-Me2C6H3
4-ClC6H4
4-FC6H4
3,4-(MeO)2C6H3
3-ClC6H4
4-(MeO)C6H4
3,5-Me2C6H3
4-ClC6H4
4-(EtO)C6H4
3-NO2C6H4
70
77
74
73
81
68
86
75
68
81
63
j
k
m
a
Yields of isolated compound.
F
F
F
F
successfully employed. The synthesis of 7aek had to be carried out
at 60e70 ꢀC to achieve a good site-selectivity. Mixtures of mono-
and diarylated products were obtained when the reactions were
carried out at higher temperatures. All attempts to achieve site-
selective SuzukieMiyaura reactions of fluorinated bis(triflate) 4c
failed, due to the formation of regioisomeric mixtures in a 1:1 ratio.
The structures of products 7d and 7h were confirmed by 2DNMR
(COSY, NOSEY and HMBC) (Figs. 3 and 4). The structure of 7d was
independently confirmed by X-ray crystal structure analysis
(Fig. 5).28
j
a
Yield of isolated compounds.
Fig. 2. Ortep plot of 6a.
Fig. 3. 2DNMR correlations for 7d.
The one-pot reaction of 4a,b with two different arylboronic
acids (sequential addition) afforded 1,2-diarylanthraquinones 8a,b
and 2-chloro-1,2-diarylanthraquinones 8c,d (Scheme 4, Table 4).
These products contain two different aryl groups. Following the
optimized reaction conditions as given for the synthesis of 7aek,
the first step of the one-pot reactions had to be carried out at
60e70 ꢀC and the second step at 100e115 ꢀC, respectively. The
structure of 8d was independently confirmed by X-ray crystal
structure analysis (Fig. 6).28
Scheme 3. Synthesis of 7aek. Conditions: i, for 7aef: 4a (1.0 equiv), ArB(OH)2
(1.0 equiv), Pd(PPh3)4 (3 mol %), K3PO4 (1.5 equiv), dioxane, 60 ꢀC, 30 h; for 7gek: 4b
(1.0 equiv), ArB(OH)2 (1.0 equiv), Pd(PPh3)4 (3 mol %), K3PO4 (1.5 equiv), dioxane, 70 ꢀC,
18 h.
It has been reported that the oxidative addition of the palla-
dium(0) catalyst generally occurs first at the electronically more
deficient and sterically less hindered position.29,30 The

9016
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
Table 4
Synthesis of 8aed
5
8
X
Ar1
Ar2
% (8)a
a,d
i,c
g,a
h,a
a
b
c
H
H
Cl
Cl
4-(MeO)C6H4
3-ClC6H4
4-ClC6H4
4-FC6H4
4-tBuC6H4
4-MeC6H4
4-(MeO)C6H4
4-(MeO)C6H4
65
74
78
68
d
a
Yield of isolated compounds.
Fig. 4. 2DNMR correlations for 7h (HMBC: single headed arrows, COSY: double headed
arrows).
Fig. 6. Ortep plot of 8d.
regioselective attack to position 1 of compounds 4a,b can be
explained by the fact that position 1 is more electron deficient than
position 3. In addition, a catalyst-directing effect of the carbonyl
group may play a role. Surprisingly, all attempts to achieve site-
selective Suzuki reactions of fluorinated bis(triflate) 4c proved to
be unsuccessful. A steric effect of the fluorine atom can be excluded,
as the corresponding reactions of the chlorinated bis(triflate) 4b
proceeded with very good site-selectivity. The low site-selectivity
in case of 4c might be explained by the (as compared to chlorine)
considerably strong
p-donating effect of the fluorine atom. This
effect results in an increase of the electron density at both positions
1 and 3, which results in an assimilation of the reactivity of both
positions.
Fig. 5. Ortep plot 7d.
3. Conclusion
O
Ar1
O
OTf
1) Ar1B(OH)2
2) Ar2B(OH)2
X
In conclusion, we have reported an efficient synthesis of ary-
lated anthraquinones by SuzukieMiyaura reactions of the bis(tri-
flates) of various 1,3-di(hydroxy)anthraquinones. The reactions of
the bis(triflates) of parent 1,3-(dihydroxy)anthraquinone and of 2-
chloro-1,3-di(hydroxy)anthraquinone proceeded with very good
site-selectivity in favour of the sterically more hindered, but elec-
tronically more deficient position 1. In contrast, no site-selectivity
was achieved in the corresponding reactions of the bis(triflate) of
2-fluoro-1,3-di(hydroxy)anthraquinone, presumably due to the
electronic effect of the fluorine atom.
X
Ar2
OTf
i
O
8a-d
O
4a-c
Scheme 4. Synthesis of 8a,b. Conditions: i, for 8a,b: 1) 4a (1.0 equiv), Ar1B(OH)2
(1.0 equiv), Pd(PPh3)4 (3 mol %), K3PO4 (3.0 equiv), dioxane, 60 ꢀC, 30 h; 2) Ar2B(OH)2
(1.2 equiv), Pd(PPh3)4 (3 mol %), 100 ꢀC, 5 h; for 8c,d: 1) 4b (1.0 equiv), Ar1B(OH)2
(1.0 equiv), Pd(PPh3)4 (3 mol %), K3PO4 (1.5 equiv), dioxane, 70 ꢀC, 18 h; 2) Ar2B(OH)2
(1.3 equiv), Pd(PPh3)4 (4 mol %), K3PO4 (1.5 equiv), 115 ꢀC, 12 h.

O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
9017
4. Experimental section
(ESI-TOF/MS, 70 eV): calcd for C14H7FO4 [M]þ: 258.03229; found:
258.03255.
4.1. General procedure A for the synthesis of 1,3-
dihydroxyanthracene-9,10-diones 3aec
4.2. General procedure B for the synthesis of 9,10-dioxo-9,10-
dihydroanthracene-1,3-diyl bis(trifluoromethanesulfonates)
4aec
In an oven dried Schlenck flask 1 (10 mmol) was placed under
argon diene 2aec (15 mmol, 1.5 equiv) was slowly added at 20 ꢀC.
This reaction mixture (neat) was stirred for 12 h. Then H2O and
EtOAc (25 mL each) were added. The organic and aqueous layers
were separated and the latter was extracted with EtOAc (4ꢁ25 mL).
The combined organic layers were dried over (Na2SO4), filtered and
the filtrate was concentrated in vacuo. The residue was purified by
column chromatography (EtOAc/Heptanes) to give 3aec.
To a CH2Cl2 (50 mL) solution of 1,3-dihydroxyanthracene-9,10-
diones 3aec (5.0 mmol), pyridine (1.6 mL, 20 mmol) and Tf2O
(2.1 mL, 12 mmol) were added and the reaction mixture was stirred
at 20 ꢀC under argon atmosphere for 8 h. To the reaction mixture
toluene (5 mL) was added and the solution was concentrated in
vacuo. The residue was chromatographed (EtOAc/Heptanes) with-
out aqueous work up to yield 4aec.
4.1.1. 1,3-Dihydroxyanthracene-9,10-dione (3a). Starting with
(2.37 g, 10 mmol) and diene 2a (3.9 g, 15 mmol), 3a was prepared
according to the general procedure A, as a yellow solid (1.37 g, 57%).
1
4.2.1. 9,10-Dioxo-9,10-dihydroanthracene-1,3-diyl bis(trifluorome-
thanesulfonate) (4a). Starting with 3a (1.2 g, 5.0 mmol), 4a was
prepared according to the general procedure B as a yellow solid
Mp: 173e175 ꢀC. 1H NMR (300 MHz, DMSO-d6):
d
¼6.56 (d, 1H,
J¼2.4 Hz, ArH), 7.08 (d, 1H, J¼2.4 Hz, ArH), 7.83e7.91 (m, 2H, ArH),
8.08e8.15 (m, 2H, ArH), 11.29 (s, 1H, ArOH), 12.69 (s, 1H, ArOH). 13
NMR (75.5 MHz, DMSO-d6):
¼106.7 (C), 107.6, 108.3, 125.4,
125.8 (CH), 131.9, 132.0 (C), 133.5, 133.7 (CH), 133.9, 163.8, 164.4 (C),
180.8, 184.9 (CO). IR (KBr):
(1.97 g, 78%). Mp: 164e166 ꢀC. 1H NMR (300 MHz, CDCl3):
d¼7.46
(d, 1H, J¼2.5 Hz, ArH), 7.77e7.86 (m, 2H, ArH), 8.22e8.33 (m, 3H,
C
ArH). 19F NMR (282.4 MHz, CDCl3):
(62.9 MHz, CDCl3):
CF3), 120.7, 122.0 (CH), 125.5 (C), 127.5, 128.1 (CH), 131.2, 133.5 (C),
135.0, 135.5 (CH), 137.5, 148.7, 152.2 (C), 179.6, 179.7 (CO). IR (KBr):
d
¼ꢂ73.1, ꢂ72.2. 13C NMR
d
d
¼118.6 (q, JC,F¼320.8, CF3), 118.7 (q, JC,F¼320.8,
n
¼3368 (m), 3070, 2921, 2854, 1743,
1722, 1711, 1670 (w), 1634, 1587 (m), 1547, 1537, 1512, 1485 (w),
1452, 1413 (m), 1379 (w), 1336, 1303, 1287, 1258, 1191, 1171, 1155
(m), 1094, 1061, 1029 (w), 1006 (m), 980, 923, 876 (w), 861, 799, 778
(m), 733 (w), 725 (m), 711 (s) cmꢂ1. MS (EI, 70 eV): m/z (%)¼240
([M]þ, 100), 212 (13), 184 (19), 155 (13), 127 (17). HRMS (EI, 70 eV):
calcd for C14H8O4 [M]þ: 240.04226; found: 240.042311.
n
¼3096, 3067, 2961, 2931, 2861 (w), 1677 (s), 1664, 1601 (w), 1586
(m), 1432 (s), 1331, 1316 (w), 1304, 1286 (m), 1256 (w), 1245 (m),
1203 (s), 1158 (w), 1132 (s), 1104 (m), 1046, 1015 (w), 991 (m), 937,
918 (w), 903, 869, 819, 795, 768, 757, 743, 732, 713 (m) cmꢂ1
.
GCeMS (EI, 70 eV): m/z (%)¼504 ([M]þ, 100), 440 (09), 375 (22), 279
(82), 251 (49). HRMS (EI, 70 eV): calcd for C16H6F6O8S2 [M]þ:
503.94083; found: 503.94066.
4.1.2. 2-Chloro-1,3-dihydroxyanthracene-9,10-dione (3b). Starting
with 1 (2.37 g, 10 mmol) and diene 2b (4.4 g, 15 mmol), 3b was
prepared according to the general procedure A, as a yellow solid
(1.68 g, 61%). Mp: 236e238 ꢀC. 1H NMR (300 MHz, DMSO-d6):
4.2.2. 2-Chloro-9,10-dioxo-9,10-dihydroanthracene-1,3-diyl bis(tri-
fluoromethanesulfonate) (4b). Starting with 3b (1.38 g, 5.0 mmol),
4b was prepared according to the general procedure B as a yellow
solid (1.89 g, 70%). Mp: 163e164 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼7.17 (s, 1H, ArH), 7.76e7.84 (m, 2H, ArH), 7.96e8.07 (m, 2H, ArH),
12.05 (br s, 1H, ArOH), 13.18 (s, 1H, ArOH). 13C NMR (62.9 MHz,
DMSO-d6):
¼107.4 (CH), 109.5, 112.6 (C), 126.4, 126.7 (CH), 131.9,
132.5, 132.6 (C), 134.7, 134.8 (CH), 159.8, 160.7 (C), 181.2, 186.1 (CO).
IR (KBr):
d
¼7.79e7.87 (m, 2H, ArH), 8.23e8.26 (m, 1H, ArH), 8.27e8.30 (m,
d
1H, ArH), 8.33 (s, 1H, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ72.9,
ꢂ72.7. 13C NMR (62.9 MHz, CDCl3):
¼118.5 (q, JC,F¼320.9, CF3),
d
n
¼3367 (br), 3076 (w), 1660 (s), 1651 (w), 1634, 1589, 1574
118.6 (q, JC,F¼320.7, CF3), 121.1 (CH), 126.6 (C), 127.5, 128.2 (CH),
(s), 1556, 1545, 1519, 1504, 1495, 1481, 1455 (w), 1422, 1398, 1370,
1362 (m), 1334, 1316, 1275, 1249 (s), 1192 (w), 1166 (m), 1094, 1076
(w), 1063 (m),1032, 1010, 977, 962, 902, 868, 850, 824, 795, 760 (w),
743 (m), 711 (s) cmꢂ1. MS (EI, 70 eV): m/z (%)¼276 ([M, 37Cl]þ, 29),
274 ([M, 35Cl]þ, 100), 246 (15), 218 (14), 207 (09). HRMS (ESI-TOF/
MS, 70 eV): calcd for C14H6ClO4 [MꢂH, 35Cl]L: 272.99601; found:
129.1, 131.8, 133.5, 134.0 (C), 135.1, 135.5 (CH), 145.6, 149.5 (C), 179.2,
179.9 (CO). IR (KBr):
n
¼3099, 3045 (w), 1682, 1668, 1582 (m), 1557,
1484 (w), 1441, 1434 (s), 1402 (w), 1332, 1313, 1282, 1238 (m), 1203
(s), 1098, 1054 (w), 1032, 1017 (m), 995 (w), 874, 815, 800 (m), 785,
760, 742, 708 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼540 ([M, 37Cl]þ,
10), 538 ([M, 35Cl]þ, 23), 409 (07), 382 (20), 315 (18), 313 (49), 285
(19), 257 (12), 216 (23), 69 (100). HRMS (EI, 70 eV): calcd for
272.99616; calcd for
found:274.99413.
C
14H6ClO4 [MꢂH, 37Cl]L
: 274.99355;
C
C
16H5ClF6O8S2 [M, 37Cl]þ: 539.89836; found: 539.89850; calcd for
16H5ClF6O8S2 [M, 35Cl]þ: 537.90131; found: 537.90100.
4.1.3. 2-Fluoro-1,3-dihydroxyanthracene-9,10-dione (3c). Starting
with 1 (2.37 g, 10 mmol) and diene 2c (4.1 g, 15 mmol), 3c was
prepared according to the general procedure A, as a yellow solid
(1.81 g, 70%). Mp: 295e297 ꢀC. 1H NMR (500 MHz, DMSO-d6):
4.2.3. 2-Fluoro-9,10-dioxo-9,10-dihydroanthracene-1,3-diyl bis(tri-
fluoromethanesulfonate) (4c). Starting with 3c (1.29 g, 5.0 mmol),
4c was prepared according to general procedure B as a yellow solid
(2.22 g, 85%). Mp: 140e142 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼7.34 (d, 1H, JHF¼7.6 Hz, ArH), 7.89e7.94 (m, 2H, ArH), 8.14e8.19
(m, 1H, ArH), 8.20e8.24 (m, 1H, ArH) 11.57 (br s, 1H, ArOH), 12.53 (s,
d
¼7.77e7.86 (m, 2H, ArH), 8.20e8.25 (m, 1H, ArH), 8.26e8.30 (m,
1H, ArOH). 19F NMR (282.4 MHz, CDCl3):
(125.8 MHz, DMSO-d6):
d
¼ꢂ153.6. 13C NMR
1H, ArH), 8.34 (d,1H, JHF¼6.8 Hz, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼109.0 (d, JC,F¼1.8 Hz, CH), 110.8 (d,
d
¼ꢂ73.4 (d, JF,F¼15.3 Hz, CF3), ꢂ72.5 (d, JF,F¼4.1 Hz, CF3), ꢂ128.6 to
ꢂ128.4 (m, F). 13C NMR (75.5 MHz, CDCl3):
¼118.5 (q, JC,F¼320.8,
d
JC,F¼2.7 Hz, C), 126.4, 126.6 (CH), 129.3 (d, JC,F¼3.7 Hz, C), 132.9,
133.0 (C), 134.5, 134.7 (CH), 142.9 (d, JC,F¼249.3 Hz, CF), 151.7 (d,
JC,F¼10.1 Hz, C), 152.4 (d, JC,F¼9.2 Hz, C), 181.0, 186.6 (CO). IR (KBr):
CF3),118.6 (q, JC,F¼321.3, CF3),122.5 (CH),127.0 (C),127.6,128.1 (CH),
130.9 (d, J¼4.4 Hz, C), 131.8, 133.5 (C), 135.2, 135.4 (CH), 137.0 (d,
J¼12.7 Hz, C), 140.9 (d, J¼12.7 Hz, C), 150.4 (d, J¼268.5 Hz, CF), 179.0
n
¼3354 (br), 3092, 1761, 1732 (w), 1641, 1634, 1610, 1583 (s), 1556,
1538, 1519, 1514, 1505, 1481, 1470, 1462 (w), 1439, 1403, 1362 (m),
1338, 1268 (br), 1226, 1978, 1165, 1154 (w), 1126 (s), 1090, 1061,
1036, 1013, 991 (m), 877, 861, 822 (w), 783 (br), 746, 733 (m), 712
(s) cmꢂ1. MS (EI, 70 eV): m/z (%)¼258 ([M]þ, 100), 240 (06), 230
(12), 202 (12), 193 (06), 179 (12), 139 (15), 137 (17), 125 (31). HRMS
(d, J¼1.7 Hz, CO), 179.6 (d, J¼1.7 Hz, CO). IR (KBr): ¼3061 (w), 1679,
n
1674 (m), 1608 (w), 1489 (m), 1435 (s), 1355, 1318 (m), 1293, 1268,
1247 (w), 1229, 1208, 1196, 1131 (s), 1104, 1074 (m), 1046, 1019, 986,
922, 911, 884, 834, 820 (w), 790, 761, 740 (m), 730 (w), 710 (s) cmꢂ1
.
GCeMS (EI, 70 eV): m/z (%)¼522 ([M]þ, 45), 453 (23), 338 (11), 309

9018
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
(12), 297 (88), 269 (28), 241 (19), 69 (100). HRMS (EI, 70 eV):
calcd for C16H5F7O8S2 [M]þ: 521.93086; found: 521.93143.
138.1, 138.2, 144.1, 144.2 (C), 182.1, 182.5 (CO). IR (KBr):
n
¼3052,
3029, 3016, 2916, 2852, 2735, 1907 (w), 1669 (s), 1587 (m), 1556,
1538 (w), 1515 (m), 1486, 1476, 1470, 1453, 1446, 1418 (w), 1340 (s),
1304 (m), 1268 (s), 1192, 1185, 1164, 1155, 1112, 1094, 1062, 1042,
4.3. General procedure C-1 for the synthesis of 6aeh
1018 (w), 963, 927, 896 (m), 813 (s), 798, 739 (m), 717, 707 (s) cmꢂ1
.
A 1,4-dioxane solution of 4a (0.2 mmol), arylboronic acid
(2.2 equiv), K3PO4 (3.0 equiv) and Pd(PPh3)4 (5 mol %) was heated at
100 ꢀC for 7 h under argon atmosphere. After cooling to 20 ꢀC, H2O
was added and the reaction mixture was extracted with CH2Cl2
(25ꢁ3 mL). The organic layers were dried (Na2SO4), filtered and
concentrated in vacuo. The residue was purified by column chro-
matography (EtOAc/Heptanes).
GCeMS (EI, 70 eV): m/z (%)¼388 ([M]þ, 57), 387 ([MꢂH]þ, 100), 374
(24), 373 (87), 313 (05), 281 (06). HRMS (EI, 70 eV): calcd for
C
28H19O2 [MꢂH]þ: 387.13796; found: 387.13786.
4.3.4. 1,3-Bis(4-(tert-butyl)phenyl)anthracene-9,10-dione (6d). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (78 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6d was
prepared as a yellow solid (71 mg, 75%). Mp: 243e245 ꢀC; reaction
4.3.1. 1,3-Bis(4-methoxyphenyl)anthracene-9,10-dione (6a). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (67 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6a was
prepared as an orange solid (64 mg, 76%). Mp: 205e207 ꢀC; re-
action temperature: 100 ꢀC for 7 h. 1H NMR (300 MHz, CDCl3):
temperature: 100 ꢀC for 7 h. 1H NMR (300 MHz, CDCl3):
d¼1.28 (s, 9H,
C(CH3)3), 1.33 (s, 9H, C(CH3)3), 7.21 (d, 2H, J¼8.5 Hz, ArH), 7.38e7.44
(m, 4H, ArH), 7.58e7.67 (m, 4H, ArH), 7.73 (d, 1H, J¼2.1 Hz, ArH),
8.03e8.09 (m, 1H, ArH), 8.17e8.23 (m, 1H, ArH), 8.53 (d, 1H, J¼2.1 Hz,
ArH). 13C NMR (75.5 MHz, CDCl3):
(C), 125.0, 126.1, 126.7, 127.0, 127.4, 127.9 (CH), 129.3, 133.0 (C), 133.5,
134.2 (CH), 134.8, 135.4 (C) 135.6, 136.1 (CH), 139.2, 145.1, 145.3, 150.0,
d
¼31.3, 31.5 (C (CH3)3), 34.7, 35.5
d
¼3.78 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 6.93 (br d, 4H, J¼8.7 Hz,
ArH), 7.21 (d, 2H, J¼8.7 Hz, ArH), 7.62 (d, 2H, J¼8.7 Hz, ArH),
7.64e7.69 (m, 3H, ArH), 8.04e8.10 (m, 1H, ArH), 8.17e8.23 (m, 1H,
ArH), 8.48 (d, 1H, J¼2.1 Hz, ArH). 13C NMR (62.9 MHz, CDCl3):
152.3 (C), 183.1, 183.6 (CO). IR (KBr):
n¼3094, 3074, 3041, 3032, 2962,
2947, 2931, 2902, 2867, 1906 (w), 1668 (s), 1587 (m), 1556, 1512, 1472,
1462, 1420, 1402, 1387, 1360 (w), 1342 (m), 1303, 1287 (w), 1267 (s),
1199, 1194, 1164, 1117, 1111, 1090, 1064, 1022, 1014, 979 (w), 964, 925,
899, 831, 818, 737 (m), 712 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼472
([M]þ, 28), 458 (25), 457 (60), 416 (30), 415 (100), 396 (14), 385 (05).
HRMS (EI, 70 eV): calcd for C34H32O2 [M]þ: 472.23968; found:
472.23900.
d
¼55.3, 55.4 (OCH3), 113.5, 114.6, 124.5, 126.7, 127.3, 128.5 (CH),
128.9 (C), 129.4 (CH), 130.8, 132.9 (C), 133.5, 134.2 (CH), 134.3,
134.9, 135.4 (C), 135.5 (CH), 144.8, 145.0, 159.0, 160.5 (C), 183.1,
183.7 (CO). IR (KBr):
n
¼3054, 3036, 3006, 2957, 2919, 2848, 1738,
1731 (w), 1671 (s), 1634 (w), 1606 (m), 1555 (w), 1510 (s), 1479 (w),
1463, 1454 (m), 1391, 1362 (w), 1338 (m), 1322, 1298, 1286 (w),
1270, 1258, 1242 (s), 1194 (w), 1184, 1173, 1166 (m), 1153, 1120, 1107,
1094 (w), 1025 (s), 978, 958, 933, 924, 907 (w), 838 (m), 803 (s),
716, 744, 731 (w), 711 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼420
([M]þ, 96), 419 ([MꢂH]þ, 100), 405 (09), 389 (23), 376 (16), 334
(06), 276 (05), 210 (10). HRMS (EI, 70 eV): calcd for C28H19O4
[MꢂH]þ: 419.12779; found: 419.12761.
4.3.5. 1,3-Di-m-tolylanthracene-9,10-dione (6e). Starting with 4a
(100 mg, 0.2 mmol), arylboronic acid (60 mg, 0.44 mmol), K3PO4
(127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6e was pre-
pared as a yellow solid (55 mg, 71%). Mp: 157e159 ꢀC; reaction
temperature: 100 ꢀC for 7 h. 1H NMR (300 MHz, CDCl3):
d
¼2.33 (s,
3H, CH3), 2.34 (s, 3H, CH3), 7.04e7.08 (m, 2H, ArH), 7.13e7.15 (m, 2H,
ArH), 7.24e7.29 (m, 2H, ArH), 7.43e7.46 (m, 2H, ArH), 7.59e7.67 (m,
2H, ArH), 7.71 (d, 1H, J¼2.1 Hz, ArH), 8.01e8.07 (m, 1H, ArH),
8.16e8.23 (m, 1H, ArH), 8.51 (d, 1H, J¼2.1 Hz, ArH). 13C NMR
4.3.2. 1,3-Bis(4-ethylphenyl)anthracene-9,10-dione
(6b). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (66 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6b was
prepared as a yellow solid (73 mg, 88%). Mp: 167e169 ꢀC; reaction
(75.5 MHz, CDCl3):
127.9, 128.0, 128.1, 128.7, 129.1 (CH), 129.4 (C), 129.8 (CH), 133.0 (C),
133.6, 134.3 (CH), 134.4, 135.3 (C), 135.9, 137.7 (CH), 138.4 (C), 138.9
d
¼21.5, 21.6 (CH3), 124.5, 125.3, 126.8, 127.4,
temperature: 100 ꢀC for 7 h. 1H NMR (250 MHz, CDCl3):
d¼1.17 (t,
3H, J¼7.6 Hz, CH3), 1.24 (t, 3H, J¼7.6 Hz, CH3), 2.60 (q, 2H, J¼7.6 Hz,
CH2), 2.67 (q, 2H, J¼7.7 Hz, CH2), 7.13e7.22 (m, 6H, ArH), 7.56 (d, 2H,
J¼8.3 Hz, ArH), 7.60e7.64 (m, 2H, ArH), 7.71 (d, 1H, J¼2.1 Hz, ArH),
8.02e8.06 (m, 1H, ArH), 8.16e8.20 (m, 1H, ArH), 8.50 (d, 1H,
(2C), 142.1, 145.3, 145.4 (C), 183.0, 183.5 (CO). IR (KBr):
n
¼3098,
3063, 3011, 2950, 2919, 2852, 2727 (w), 1669 (s), 1587 (m), 1556,
1538, 1495, 1485, 1462, 1454, 1445, 1417, 1377 (w), 1338, 1305 (m),
1270 (s), 1200, 1160, 1150, 1089, 1066, 1035, 1004, 997, 977, 935 (w),
897, 799 (m), 783, 709 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼388
([M]þ, 67), 387 ([MꢂH]þ, 64), 374 (32), 373 (100), 313 (05). HRMS
J¼2.1 Hz, CH2). 13C NMR (62.9 MHz, CDCl3):
¼14.3, 14.4 (CH3), 27.5,
d
27.6 (CH2), 123.9, 125.7, 126.1, 126.3, 126.5, 127.1, 127.6 (CH), 128.1,
128.2, 131.9 (C), 132.4, 133.1 (CH), 133.7, 134.3 (C), 134.7 (CH), 138.3,
142.1, 144.1, 144.2, 144.3 (C), 182.0, 182.4 (CO). IR (KBr):
n
¼3054,
(EI, 70 eV): calcd for
387.13820.
C
28H19O2 [MꢂH]þ: 387.13796; found:
3025, 2960, 2929, 2869 (w), 1668, 1588, 1580 (m), 1556, 1513, 1453,
1427,1410,1386 (w),1340,1307 (m),1270 (s),1186,1165,1094,1062,
1050, 1018, 959, 927, 900, 834 (w), 818 (s), 798, 739 (m), 710
(s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼416 ([M]þ, 36), 415 ([MꢂH]þ,
45), 400 (09), 387 (100), 372 (10). HRMS (EI, 70 eV): calcd for
4.3.6. 1,3-Bis(3,5-dimethylphenyl)anthracene-9,10-dione (6f). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (66 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6f was
prepared as a yellow solid (68 mg, 82%). Mp: 196e198 ꢀC; reaction
C
30H23O2 [MꢂH]þ: 415.16926; found: 415.168812.
temperature: 100 ꢀC for 7 h.1H NMR (300 MHz, CDCl3):
d
¼2.30 (s, 6H,
4.3.3. 1,3-Di-p-tolylanthracene-9,10-dione (6c). Starting with 4a
(100 mg, 0.2 mmol), arylboronic acid (60 mg, 0.44 mmol), K3PO4
(127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6c was pre-
pared as a yellow solid (62 mg, 80%). Mp: 198e199 ꢀC; Reaction
2CH3), 2.31 (s, 6H, 2CH3), 6.88 (br s, 2H, ArH), 6.97 (br s,1H, ArH), 6.99
(br s,1H, ArH), 7.23 (br s, 2H, ArH), 7.61e7.68 (m, 2H, ArH), 7.70 (d,1H,
J¼2.1 Hz, ArH), 8.03e8.08 (m, 1H, ArH), 8.18e8.23 (m, 1H, ArH), 8.51
(d, 1H, J¼2.1 Hz, ArH). 13C NMR (75.5 MHz, CDCl3):
¼20.3, 20.4
d
temperature: 100 ꢀC for 7 h. 1H NMR (300 MHz, CDCl3):
d
¼2.32 (s,
(2CH3), 124.1, 124.2, 124.8, 125.7, 126.3, 128.0 (CH), 128.3 (C), 129.5
(CH), 131.9 (C), 132.4, 133.1 (CH), 133.8, 134.1 (C), 134.8 (CH), 136.5,
3H, CH3), 2.38 (s, 3H, CH3), 7.15e7.19 (m, 6H, ArH), 7.56 (d, 2H,
J¼8.2 Hz, ArH), 7.61e7.69 (m, 2H, ArH), 7.71 (d, 1H, J¼2.1 Hz, ArH),
8.03e8.09 (m, 1H, ArH), 8.18e8.24 (m, 1H, ArH), 8.51 (d, 1H,
137.4, 137.7, 141.1, 144.3, 144.4 (C), 181.9, 182.6 (CO). IR (KBr):
n
¼2997,
2917, 2850, 2734 (w), 1680, 1665 (s), 1644, 1633 (w), 1588 (s), 1556,
1538, 1504, 1494, 1407, 1463, 1454, 1343 (w), 1377, 1352, 1305 (m),
1289, 1273 (s), 1240, 1203, 1154, 1117, 1095, 1040, 1015, 974, 944, 927,
909, 899, 883, 860 (w), 841 (m), 822, 794, 779, 738 (w) cmꢂ1. GCeMS
J¼2.1 Hz, ArH). 13C NMR (62.9 MHz, CDCl3):
¼20.2, 20.4 (CH3),
d
123.9, 125.7, 126.1, 126.3, 126.9, 127.8 (CH), 128.2 (C), 128.8 (CH),
131.9 (C) 132.5, 133.2 (CH), 133.8, 134.3, 134.5 (C), 134.7 (CH), 135.9,

O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
9019
(EI, 70 eV): m/z (%)¼416 ([M]þ, 27), 402 (31), 401 (100). HRMS (EI,
8.01e8.04 (m, 1H, ArH), 8.17e8.20 (m, 1H, ArH), 8.31 (s, 1H, ArH).
13C NMR (62.9 MHz, CDCl3):
129.0, 129.1, 129.2, 129.8 (CH), 131.0, 132.5, 132.6 (C), 133.8, 134.4
(CH), 134.6, 135.6, 136.5, 137.0, 138.6, 140.8, 143.2, 146.4 (C), 182.4,
70 eV): calcd for C30H24O2 [M]þ: 416.17708; found: 416.17677.
d
¼21.3, 21.6 (2CH3), 126.7, 127.6, 127.8,
4.3.7. 1,3-Bis(4-chlorophenyl)anthracene-9,10-dione (6g). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (69 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6g was
prepared as a yellow solid (72 mg, 84%). Mp: 173e175 ꢀC; reaction
182.9 (CO). IR (KBr):
n
¼3081, 3035, 3027, 3011, 2920, 2853, 1901
(w), 1673 (s), 1652, 1613, 1589 (w), 1569 (m), 1512, 1454, 1377 (w),
1337, 1292, 1280, 1257 (s), 1182, 1170, 1155, 1112, 1092, 1039, 1021
(w), 963 (m), 940 (w), 920 (m), 896, 846 (w), 814 (s), 795, 762 (m),
733 (w), 711 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼424 ([M, 37Cl]þ,
17), 422 ([M, 35Cl]þ, 49), 409 (37), 407 (100), 313 (09), 210 (10).
HRMS (EI, 70 eV): calcd for C28H19ClO2 [M, 37Cl]þ: 424.10386;
found: 424.10384; calcd for C28H19ClO2 [M, 35Cl]þ: 422.10681;
found: 422.10549.
temperature: 100 ꢀC for 7 h. 1H NMR (300 MHz, CDCl3):
d
¼7.21 (d,
2H, J¼8.5. Hz, ArH), 7.35e7.43 (m, 4H, ArH), 7.61 (d, 2H, J¼8.7. Hz,
ArH), 7.66 (d, 1H, J¼2.1. Hz, ArH), 7.69e7.72 (m, 2H, ArH), 8.04e8.10
(m, 1H, ArH), 8.21e8.27 (m, 1H, ArH), 8.54 (d, 1H, J¼2.1 Hz, ArH). 13
C
NMR (62.9 MHz, CDCl3):
129.5 (CH), 129.6, 132.8 (C), 133.5, 133.9, 134.5 (CH), 134.6 (C), 135.4
(2C), 135.5, 136.7, 140.2, 144.0, 144.2 (C), 181.9, 182.6 (CO). IR (KBr):
d
¼125.5, 126.9, 127.4, 128.4, 128.6, 129.4,
n
¼3054, 3028, 2953, 2920, 2851 (w), 1673 (s), 1651, 1644, 1633 (w),
4.4.2. 2-Chloro-1,3-bis(3,5-dimethylphenyl)anthracene-9,10-dione
(6j). Starting with 4b (70 mg, 0.13 mmol), arylboronic acid (47 mg,
0.31 mmol), K3PO4 (83 mg, 0.39 mmol) and Pd(PPh3)4 (11 mg,
7 mol %), 6j was prepared as a yellow solid (45 mg, 77%). Mp:
228e230 ꢀC. Reaction temperature: 115 ꢀC; for 10 h. 1H NMR
1584 (s), 1556, 1538 (w), 1488, 1464, 1455, 1447 (m), 1416, 1394,
1377 (w), 1362, 1313, 1298, 1285 (m), 1271 (s), 1194, 1180, 1165, 1159,
1107 (w), 1090 (s), 1046, 1033 (w), 1011 (s), 963, 951, 925, 909, 864
(m), 814 (s), 797, 741, 724 (m), 709 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z
(%)¼432 ([M, 37Cl, 37Cl]þ, 16), 430 ([M, 35Cl, 37Cl]þ, 33), 429 ([MꢂH,
35Cl, 37Cl]þ, 73), 428 ([M, 35Cl, 35Cl]þ, 52), 427 ([MꢂH, 35Cl, 35Cl]þ,
100), 414 (11), 394 (10), 393 (30), 363 (06), 300 (29), 274 (09). HRMS
(EI, 70 eV): calcd for C26H13O2Cl2 [MꢂH, 35Cl, 37Cl]þ: 429.02576;
found: 429.02706; calcd for C26H13O2Cl2 [MꢂH, 35Cl, 35Cl]þ:
427.02871; found: 427.028375.
(300 MHz, CDCl3):
d
¼2.32 (s, 6H, 2CH3), 2.33 (s, 6H, 2CH3), 7.76 (br
s, 2H, ArH), 7.02 (br s, 1H, ArH), 7.04e7.06 (m, 3H, ArH), 7.63e7.72
(m, 2H, ArH), 8.01e8.07 (m, 1H, ArH), 8.19e8.22 (m, 1H, ArH), 8.29
(s, 1H, ArH). 13C NMR (75.5 MHz, CDCl3):
d
¼21.4, 21.5 (4CH3), 126.6,
126.7, 127.0, 127.7, 129.2, 129.6, 130.2 (CH), 131.0, 132.4, 132.7 (C),
133.7, 134.4 (CH), 134.7, 137.0, 137.9, 138.5, 139.3, 140.7, 143.4, 146.7
(C),182.3,183.0 (CO). IR (KBr):
n
¼3068, 2995, 2917, 2852, 2733,1732
4.3.8. 1,3-Bis(4-fluorophenyl)anthracene-9,10-dione (6h). Starting
with 4a (100 mg, 0.2 mmol), arylboronic acid (62 mg, 0.44 mmol),
K3PO4 (127 mg, 0.6 mmol) and Pd(PPh3)4 (12 mg, 5 mol %), 6h was
prepared as yellow solid (62 mg, 78%). Mp: 187e189 ꢀC; reaction
(w), 1674 (s), 1633, 1589 (w), 1573 (s), 1470, 1455, 1434, 1380, 1375
(w), 1350 (s), 1301 (w), 1287 (s), 1254 (m), 1227, 1209, 1161, 1124,
1117, 1091, 965, 947, 895, 846, 821, 792, 783, 758, 727 (w), 709
(s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼452 ([M, 37Cl]þ, 10), 450 ([M,
35Cl]þ, 26), 437 (38), 436 (34), 435 (100), 326 (04), 225 (05). HRMS
(ESI-TOF/MS, 70 eV): calcd for C30H24ClO2 [MþH, 37Cl]þ: 453.14441;
found: 453.14498; calcd for C30H24ClO2 [MþH, 35Cl]þ: 451.14593;
found: 451.14609.
temperature: 100 ꢀC for
7
h. 1H NMR (300 MHz, CDCl3):
d
¼7.02e7.15 (m, 4H, ArH), 7.20e7.26 (m, 2H, ArH), 7.61e7.69 (m,
5H, ArH), 8.02e8.07 (m, 1H, ArH), 8.18e8.24 (m, 1H, ArH), 8.49 (d,
1H, J¼2.1 Hz, ArH). 19F NMR (282.4 MHz, CDCl3):
¼ꢂ114.8, ꢂ112.4.
d
13C NMR (75.5 MHz, CDCl3):
d
¼115.1 (d, JC,F¼21.5 Hz, CH), 116.2 (d,
JC,F¼21.5 Hz, CH), 125.4, 126.9, 127.4 (CH), 129.1 (d, JC,F¼8.3 Hz, CH),
129.4 (C), 129.8 (d, JC,F¼8.3 Hz, C), 132.8 (C), 133.8, 134.4 (CH), 134.5
(d, JC,F¼3.3 Hz, C), 134.6, 135.4 (C), 135.6 (CH), 137.7 (d, JC,F¼3.9 Hz,
C), 144.2, 144.4 (C), 162.3 (d, JC,F¼246.5 Hz, CF), 163.5 (d,
4.4.3. 2-Chloro-1,3-bis(4-chlorophenyl)anthracene-9,10-dione
(6k). Starting with 4b (70 mg, 0.13 mmol), arylboronic acid (49 mg,
0.31 mmol), K3PO4 (83 mg, 0.39 mmol) and Pd(PPh3)4 (11 mg,
7 mol %), 6k was prepared as a yellow solid (43 mg, 71%). Mp:
227e229 ꢀC; reaction temperature: 115 ꢀC; for 10 h. 1H NMR
JC,F¼249.3 Hz, CF), 183.0, 183.2 (CO). IR (KBr): ¼3077, 3056, 2920,
n
2851 (w), 1673, 1666 (s), 1644, 1634 (w), 1602, 1590 (s), 1556, 1538
(w),1510,1506 (s), 1481,1471, 1462,1447, 1427,1404, 1379 (w),1339,
1316, 1299 (m), 1271 (s), 1248 (w), 1226 (s), 1194, 1166 (m), 1155 (s),
1098,1069, 1013, 965, 944, 907, 851 (w), 838, 824, 804, 792, 774, 741
(m), 722 (w), 705 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼396 ([M]þ,
50), 395 ([MꢂH]þ, 100), 377 (04), 336 (04), 281 (05), 207 (10).
HRMS (EI, 70 eV): calcd for C26H13O2F2 [MꢂH]þ: 395.08781; found:
395.08800.
(300 MHz, CDCl3):
ArH), 7.65e7.74 (m, 2H, ArH), 7.99e8.05 (m, 1H, ArH), 8.17e8.23 (m,
1H, ArH), 8.31 (s, 1H, ArH). 13C NMR (75.5 MHz, CDCl3):
d¼7.07 (d, 2H, J¼8.5 Hz, ArH), 7.36e7.45 (m, 6H,
d¼126.7,
127.6, 128.7, 128.8, 129.4, 130.0, 130.6 (CH), 131.3, 132.5, 132.7, 133.6
(C), 134.1 (CH), 134.3 (C), 134.6 (CH), 135.0, 136.5, 137.6, 140.4, 142.0,
145.3 (C), 182.2, 182.4 (CO). IR (KBr):
n
¼3093, 3075, 3046, 2921,
2851, 1897 (w), 1670 (s), 1589 (w), 1567 (m), 1538 (w), 1489 (m),
1363, 1291, 1280, 1259 (s), 1184, 1173, 1158, 1120 (w), 1088 (s), 974
(w), 963, 951, 938 (m), 901, 849 (w), 823, 818 (s), 797 (m), 760, 738,
729 (w), 711, 705 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼468 ([M,
37Cl, 37Cl, 37Cl]þ, 04), 466 ([M, 35Cl, 37Cl, 37Cl]þ, 28), 464 ([M, 35Cl,
35Cl, 37Cl]þ, 82), 463 ([MꢂH, 35Cl, 35Cl, 37Cl]þ, 100), 462 ([M, 35Cl,
35Cl, 35Cl]þ, 80), 461 ([MꢂH, 35Cl, 35Cl, 35Cl]þ, 86), 431 (10), 430 (15),
429 (54), 428 (23), 427 (78), 391 (05), 300 (20), 298 (11). HRMS (EI,
70 eV): calcd for C26H12Cl3O2 [MꢂH, 35Cl, 35Cl, 35Cl]þ: 460.98974;
found: 460.98984; calcd for C26H13Cl3O2 [M, 35Cl, 35Cl, 35Cl]þ:
461.99756; found: 461.99602; calcd for C26H13Cl3O2 [M, 35Cl, 35Cl,
37Cl]þ: 463.99461; found: 463.99366; calcd for C26H13Cl3O2 [M,
35Cl, 37Cl, 37Cl]þ: 465.99166; found: 465.99123.
4.4. General procedure C-2 for the synthesis of 6iel
A 1,4-dioxane solution of 4b (0.13 mmol), arylboronic acid
(2.4 equiv), K3PO4 (3.0 equiv) and Pd(PPh3)4 (7 mol %) was heated at
115 ꢀC for 10 h under argon atmosphere. After cooling to 20 ꢀC, H2O
was added and the reaction mixture was extracted with CH2Cl2
(25ꢁ3 mL). The organic layers were dried (Na2SO4), filtered and
concentrated in vacuo. The residue was purified by column chro-
matography (EtOAc/Heptanes).
4.4.1. 2-Chloro-1,3-di-p-tolylanthracene-9,10-dione
(6i). Starting
with 4b (70 mg, 0.13 mmol), arylboronic acid (42 mg, 0.31 mmol),
K3PO4 (83 mg, 0.39 mmol) and Pd(PPh3)4 (11 mg, 7 mol %), 6i was
prepared as a yellow solid (47 mg, 85%). Mp: 213e215 ꢀC; reaction
4.4.4. 2-Chloro-1,3-bis(4-fluorophenyl)anthracene-9,10-dione
(6l). Starting with 4b (70 mg, 0.13 mmol), arylboronic acid (44 mg,
0.31 mmol), K3PO4 (83 mg, 0.39 mmol) and Pd(PPh3)4 (11 mg,
7 mol %), 6l was prepared as yellow solid (42 mg, 75%). Mp:
203e205 ꢀC. Reaction temperature: 115 ꢀC; for 10 h. 1H NMR
temperature: 115 ꢀC for 10 h. 1H NMR (300 MHz, CDCl3):
d¼2.36
(s, 3H, CH3), 2.41 (s, 3H, CH3), 7.03 (d, 2H, J¼7.9 Hz, ArH), 7.21e7.27
(m, 4H, ArH), 7.35 (d, 2H, J¼7.9 Hz, ArH), 7.62e7.70 (m, 2H, ArH),
(300 MHz, CDCl3):
d
¼7.07e7.17 (m, 6H, ArH), 7.40e7.44 (m, 2H,

9020
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
ArH), 7.64e7.72 (m, 2H, ArH), 7.99e8.02 (m, 1H, ArH), 8.17e8.20 (m,
JC,F¼255.4 Hz, CF), 182.4, 182.5 (CO). IR (KBr): ¼3055, 3030, 2992,
n
1H, ArH), 8.30 (s, 1H, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ114.2,
2943, 2920, 2860 (w), 1672 (s), 1613 (w), 1588 (m), 1552, 1477, 1454,
1440, 1395, 1380 (w), 1344 (s), 1302 (m), 1270 (s), 1196, 1184, 1171,
1156, 1116, 1103, 1038, 1022, 1011, 963, 921, 894, 846 (w), 818 (s),
795 (m), 755 (s), 730 (w), 712 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼
406 ([M]þ, 41), 405 (84), 392 (32), 391 (100). HRMS (ESI-TOF/MS,
70 eV): calcd for C28H20FO2 [MþH]þ: 407.14418; found: 407.14353;
calcd for C28H19FNaO2 [MþNa]þ: 429.12613; found: 429.12559.
ꢂ112.4, 13C NMR (62.9. MHz, CDCl3):
d
¼115.5 (d, JC,F¼21.7 Hz, CH),
115.6 (d, JC,F¼21.7 Hz, CH), 126.8, 127.6 (CH), 129.7 (d, JC,F¼8.0 Hz,
CH), 130.0 (CH), 131.1 (d, JC,F¼8.3 Hz, CH), 131.3, 132.5, 132.6 (C),
134.0 (CH), 134.2 (d, JC,F¼4.5 Hz, C), 134.4 (C), 134.5 (CH), 135.0 (d,
JC,F¼3.6 Hz, C), 140.8, 142.2, 145.4 (C), 162.2 (d, JC,F¼246.6 Hz, CF),
162.9 (d, JC,F¼249.1 Hz, CF), 182.3, 182.6 (CO). IR (KBr): ¼3068,
n
2958, 2919, 2850, 1884 (w), 1673 (s), 1601, 1589, 1572, 1542 (w),
1509 (m), 1478, 1470, 1464, 1455, 1427, 1417, 1403, 1373, 1366 (w),
1337, 1292 (s), 1172, 1163, 1134, 1116 (w), 1092 (s), 1040, 1013, 960,
930, 918, 901 (w), 836, 829, 817, 802 (s), 787, 773, 760 (m), 737 (w),
713 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼432 ([M, 37Cl]þ, 42), 430
([M, 35Cl]þ, 63), 429 ([MꢂH, 35Cl]þ, 100), 395 (09), 365 (05), 338
(05), 336 (06). HRMS (ESI-TOF/MS, 70 eV): calcd for C26H14ClF2O2
[MþH, 35Cl]þ: 431.06449; found: 431.06465.
4.5.3. 1,3-Bis(4-chlorophenyl)-2-fluoroanthracene-9,10-dione
(6o). Starting with 4c (52 mg, 0.1 mmol), arylboronic acid (35 mg,
0.22 mmol), K3PO4 (127 mg, 0.3 mmol) and Pd(PPh3)4 (4 mg,
6 mol %), 6o was prepared as a yellow solid (34 mg, 76%). Mp:
258e260 ꢀC; reaction temperature: 110 ꢀC for 8 h. 1H NMR
(300 MHz, CDCl3):
d
¼7.15e7.19 (m, 2H, ArH), 7.39e7.44 (m, 4H,
ArH), 7.52e7.56 (m, 2H, ArH), 7.65e7.75 (m, 2H, ArH), 8.00e8.07
(m, 1H, ArH), 8.20e8.26 (m, 1H, ArH), 8.46 (d, 1H, JHF¼7.6 Hz, ArH).
4.5. General procedure C-3 for the synthesis of 6meq
19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ107.0. 13C NMR (62.9 MHz,
CDCl3):
d
¼127.0, 127.4, 128.7, 129.1 (CH), 130.0 (d, JC,F¼0.9 Hz, CH),
A 1,4-dioxane solution of 4c (0.1 mmol), arylboronic acid
(2.2 equiv), K3PO4 (3.0 equiv) and Pd(PPh3)4 (6 mol %) was heated at
110 ꢀC for 8 h under argon atmosphere. After cooling to 20 ꢀC, H2O
was added and the reaction mixture was extracted with CH2Cl2
(25ꢁ3 mL). The organic layers were dried (Na2SO4), filtered and
concentrated in vacuo. The residue was purified by column chro-
matography (EtOAc/Heptanes).
130.2 (d, JC,F¼5.0 Hz, CH), 130.4 (d, JC,F¼3.7 Hz, CH), 130.7 (C), 131.0
(d, JC,F¼4.1 Hz, C), 131.8 (d, JC,F¼3.2 Hz, C), 132.0 (d, JC,F¼1.8 Hz, C),
132.5 (d, JC,F¼1.4 Hz, C),132.6 (C),133.4 (d, JC,F¼16.5 Hz, C),134.0 (C),
134.1, 134.4 (CH), 134.5, 135.5 (C), 160.4 (d, JC,F¼256.4 Hz, CF), 182.1
(d, JC,F¼1.4 Hz, CO), 182.3 (d, JC,F¼2.3 Hz, CO). IR (KBr): ¼3092,
n
3065, 2918, 2850, 1902 (w), 1674, 1667, 1585, 1574 (m), 1548, 1538,
1520 (w), 1493 (m), 1471, 1455, 1435, 1385 (w), 1339 (s), 1299 (m),
1274 (s), 1211, 1184, 1174, 1160 (w), 1089 (m), 1042 (w), 1010 (m),
964, 957, 941, 907, 868 (w), 828 (s), 813 (m), 796 (w), 761 (s), 737,
730 (w), 712 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼450 ([M, 37Cl,
37Cl]þ, 05), 448 ([M, 35Cl, 37Cl]þ, 39), 446 ([M, 35Cl, 35Cl]þ, 68), 455
(100), 413 (29), 411 (76), 331 (04), 318 (15), 281 (23). HRMS (ESI-
TOF/MS, 70 eV): calcd for C26H13Cl2FNaO2 [MþNa, 35Cl, 37Cl]þ:
471.01453; found: 471.01515; calcd for C26H13Cl2FNaO2 [MþNa,
35Cl, 35Cl]þ: 469.01646; found: 469.01688.
4.5.1. 1,3-Bis(4-ethylphenyl)-2-fluoroanthracene-9,10-dione
(6m). Starting with 4c (52 mg, 0.1 mmol), arylboronic acid (33 mg,
0.22 mmol), K3PO4 (127 mg, 0.3 mmol) and Pd(PPh3)4 (4 mg,
6 mol %), 6m was prepared as a yellow solid (39 mg, 90%). Mp:
258e259 ꢀC; reaction temperature: 110 ꢀC for 8 h. 1H NMR
(300 MHz, CDCl3):
d
¼1.18 (t, 3H, J¼7.6 Hz, CH3), 1.24 (t, 3H, J¼7.6 Hz,
CH3), 2.68e2.73 (m, 4H, 2CH2), 7.12e7.15 (m, 2H, ArH), 7.20e7.27
(m, 4H, ArH), 7.49e7.53 (m, 2H, ArH), 7.57e7.66 (m, 2H, ArH),
7.97e8.03 (m, 1H, ArH), 8.13e8.20 (m, 1H, ArH), 8.43 (d, 1H,
4.5.4. 1,3-Bis(3-chlorophenyl)-2-fluoroanthracene-9,10-dione
(6p). Starting with 4c (52 mg, 0.1 mmol), arylboronic acid (35 mg,
0.22 mmol), K3PO4 (127 mg, 0.3 mmol) and Pd(PPh3)4 (4 mg,
6 mol %), 6p was prepared as yellow solid (73 mg, 81%). Mp:
147e149 ꢀC. Reaction temperature: 110 ꢀC for 8 h. 1H NMR
JHF¼7.7 Hz, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ106.8. 13C NMR
(62.9 MHz, CDCl3):
d
¼15.1, 15.4 (CH3), 28.7 (2CH2), 126.8, 127.4,
127.8, 128.3 (CH), 128.5 (d, JC,F¼0.9 Hz, CH), 129.2 (d, JC,F¼3.7 Hz,
CH), 129.8 (d, JC,F¼6.0 Hz, CH), 130.9 (d, JC,F¼4.1 Hz, C), 131.2 (d,
JC,F¼1.8 Hz, C), 131.4 (d, JC,F¼3.7 Hz, C), 131.5 (d, JC,F¼1.4 Hz, C), 132.2
(d, JC,F¼20.1 Hz, C),132.7 (C),133.7,134.2 (CH),134.4 (d, JC,F¼16.5 Hz,
C), 134.7, 143.5, 145.5 (C), 160.8 (d, JC,F¼255.4 Hz, CF), 182.4, 182.5
(300 MHz, CDCl3):
d
¼7.09e7.15 (m, 1H, ArH), 7.23 (br s, 1H, ArH),
7.33e7.41 (m, 4H, ArH), 7.44e7.50 (m, 1H, ArH), 7.59 (br s, 1H, ArH),
7.64e7.74 (m, 2H, ArH), 7.99e8.06 (m, 1H, ArH), 8.19e8.25 (m, 1H,
ArH), 8.46 (d, 1H, JHF¼7.6 Hz, ArH). 19F NMR (282.4 MHz, CDCl3):
(CO). IR (KBr):
n
¼3093, 3056, 2993, 2921, 2851, 1902 (w),1674, 1667,
1586 (m), 1547 (w), 1493 (m), 1435, 1384 (w) 1339 (s), 1300 (w),
1273 (s), 1211, 1184, 1172, 1161 (w), 1089 (m), 1042 (w), 1011, 965
(m), 957, 908, 863 (w), 828 (m), 814, 797 (w), 761 (s), 737, 731 (w),
712 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼434 ([M]þ, 18), 433 (16),
406 (32), 405 (100), 390 (10). HRMS (ESI-TOF/MS, 70 eV): calcd for
d
¼ꢂ106.4. 13C NMR (62.9 MHz, CDCl3):
¼126.8 (d, JC,F¼1.4 Hz, CH),
d
127.0 (CH), 127.3 (d, JC,F¼3.2 Hz, CH), 127.5, 128.1 (CH), 128.6 (d,
JC,F¼1.4 Hz, CH), 129.2 (d, JC,F¼4.1 Hz, CH), 129.3, 129.6, 130.1 (CH),
130.4 (d, JC,F¼5.5 Hz, CH), 130.7 (C), 131.0 (d, JC,F¼4.1 Hz, C), 131.9 (d,
JC,F¼3.2 Hz, C), 132.6 (C), 133.2 (d, JC,F¼16.5 Hz, C), 134.1 (CH), 134.3,
134.4 (C), 134.5 (CH), 134.6 (d, JC,F¼20.1 Hz, C), 135.3 (d, JC,F¼1.8 Hz,
C), 135.8 (d, JC,F¼1.4 Hz, C), 160.4 (d, JC,F¼256.8 Hz, CF), 182.0 (d,
C
C
30H24FO2 [MþH]þ: 435.17548; found: 435.17534; calcd for
30H23FNaO2 [MþNa]þ: 457.15743; found: 457.15714.
JC,F¼0.9 Hz, CO), 181.1 (d, JC,F¼1.8 Hz, CO). IR (KBr): ¼3066, 2918,
n
4.5.2. 2-Fluoro-1,3-di-p-tolylanthracene-9,10-dione (6n). Starting
with 4c (52 mg, 0.1 mmol), arylboronic acid (30 mg, 0.22 mmol),
K3PO4 (127 mg, 0.3 mmol) and Pd(PPh3)4 (4 mg, 6 mol %), 6n was
prepared as a yellow solid (36 mg, 88%). Mp: 235e237 ꢀC; reaction
2849 (w), 1673 (s), 1588, 1568 (m), 1557, 1539, 1480, 1393 (w), 1337
(s), 1302 (m), 1271 (s), 1211, 1176, 1110, 1077, 1043, 1020, 998 (w),
976 (m), 929, 886, 869, 824, 763, 743 (w), 712, 705 (s) cmꢂ1. GCeMS
(EI, 70 eV): m/z (%)¼450 ([M, 37Cl, 37Cl]þ, 06), 448 ([M, 35Cl, 37Cl]þ,
32), 446 ([M, 35Cl, 35Cl]þ, 49), 413 (37), 411 (100), 318 (16), 281 (10).
HRMS (ESI-TOF/MS, 70 eV): calcd for C26H14Cl2FO2 [MþH, 35Cl,
37Cl]þ: 447.03494; found: 447.03356; calcd for C26H13Cl2FO2 [MþH,
35Cl, 35Cl]þ: 449.03258; found: 449.01378.
temperature: 110 ꢀC for 8 h. 1H NMR (300 MHz, CDCl3):
d
¼2.32 (s,
3H, CH3), 2.38 (s, 3H, CH3), 7.10e7.14 (m, 2H, ArH), 7.18e7.25 (m, 4H,
ArH), 7.46e7.50 (m, 2H, ArH), 7.57e7.68 (m, 2H, ArH), 7.97e8.04 (m,
1H, ArH), 8.14e8.21 (m, 1H, ArH), 8.42 (d, 1H, JHF¼7.6 Hz, ArH). 19
F
NMR (282.4 MHz, CDCl3):
d
¼ꢂ107.0. 13C NMR (62.9 MHz, CDCl3):
d¼21.3, 21.5 (CH3), 126.6, 127.4 (CH), 128.4 (d, JC,F¼0.9 Hz, CH), 129.0
4.5.5. 2-Fluoro-1,3-diphenylanthracene-9,10-dione
(6q). Starting
(CH), 129.1 (d, JC,F¼4.1 Hz, CH), 129.4 (CH), 129.8 (d, JC,F¼5.5 Hz, CH),
130.9 (d, JC,F¼4.1 Hz, C), 131.0 (d, JC,F¼1.8 Hz, C), 131.3 (d, JC,F¼1.4 Hz,
C), 131.4 (d, JC,F¼3.2 Hz, C), 132.1 (d, JC,F¼20.1 Hz, C), 132.7 (C), 133.8,
134.2 (CH), 134.4 (d, JC,F¼16.9 Hz, C), 134.7, 137.4, 139.2 (C), 160.8 (d,
with 4c (52 mg, 0.1 mmol), arylboronic acid (27 mg, 0.22 mmol),
K3PO4 (127 mg, 0.3 mmol) and Pd(PPh3)4 (4 mg, 6 mol %), 6q was
prepared as a yellow solid (31 mg, 82%). Mp: 198e200 ꢀC. Reaction
temperature: 110 ꢀC for
8
h. 1H NMR (500 MHz, CDCl3):

O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
9021
d
¼7.22e7.24 (m, 2H, ArH), 7.34e7.45 (m, 6H, ArH), 7.58e7.60 (m,
GCeMS (EI, 70 eV): m/z (%)¼460 ([M]þ, 36), 446 (24), 445 (100),
327 (20), 329 (100), 298 (11), 284 (44), 273 (16), 239 (07), 226 (11).
HRMS (EI, 70 eV): calcd for C23H15F3O5S [M]þ: 460.05868; found:
460.05750.
2H, ArH), 7.61e7.67 (m, 2H, ArH), 8.00e8.02 (m,1H, ArH), 8.18e8.20
(m, 1H, ArH), 8.45 (d, 1H, JHF¼7.6 Hz, ArH). 19F NMR (282.4 MHz,
CDCl3):
d
¼ꢂ106.8. 13C NMR (125.8 MHz, CDCl3):
¼126.9, 127.5,
d
127.8, 128.3, 128.6, 128.8, 129.1 (CH), 129.2 (d, JC,F¼3.7 Hz, CH), 130.2
(d, JC,F¼5.5 Hz, CH), 131.0 (d, JC,F¼3.7 Hz, C), 131.7 (d, JC,F¼3.7 Hz, C),
132.1 (d, JC,F¼20.2 Hz, C), 132.7 (C), 133.8 (CH), 133.9 (d, JC,F¼1.3 Hz,
C), 134.2 (CH), 134.3 (d, JC,F¼3.8 Hz, C), 134.5 (d, JC,F¼16.5 Hz, C),
4.6.3. 4-(4-Chlorophenyl)-9,10-dioxo-9,10-dihydroanthracen-2-yl
trifluoromethanesulfonate (7c). Starting with 4a (100 mg,
0.2 mmol), arylboronic acid (31 mg, 0.2 mmol), K3PO4 (64 mg,
0.3 mmol) and Pd(PPh3)4 (07 mg, 3 mol %), 7c was prepared as
a yellow solid (69 mg, 74%). Mp: 150e152 ꢀC; reaction temperature:
134.7 (C), 160.7 (d, JC,F¼255.1 Hz, CF), 182.4 (2CO). IR (KBr): ¼3061,
n
2919, 2850 (w), 1673, 1668 (s), 1651,1633 (w), 1587, 1580, 1574, 1556
(m), 1538, 1519, 1495, 1477, 1471, 1454, 1444, 1435, 1406 (w), 1339,
1302, 1268 (s), 1207, 1172, 1159, 1103, 1073, 1035, 1027, 1012, 967,
60 ꢀC for 30 h. 1H NMR (300 MHz, CDCl3):
d
¼7.14e7.20 (m, 2H, ArH),
7.36e7.42 (m, 3H, ArH), 7.70e7.77 (m, 2H, ArH), 8.02e8.08 (m, 1H,
962, 913, 900, 866, 849, 839, 821, 799, 777 (w), 737, 712 (s) cm cmꢂ1
.
ArH), 8.21e8.26 (m, 2H, ArH). 19F NMR (282.4 MHz, CDCl3):
GCeMS (EI, 70 eV): m/z (%)¼378 ([M,]þ, 56), 377 (100), 318 (05),
244 (05) HRMS (ESI-TOF/MS, 70 eV): calcd for C26H16FO2 [MþH]þ:
379.11288; found: 479.11260.
d
¼ꢂ72.6. 13C NMR (62.9 MHz, CDCl3):
¼118.7 (q, JC,F¼320.9, CF3),
d
118.9, 126.2, 126.6, 127.6, 128.3, 128.7 (CH), 129.5, 131.4, 133.1 (C),
133.2 (CH), 133.3 (C), 134.0 (CH), 136.4, 137.3, 145.6, 150.6 (C), 180.3,
180.9 (CO). IR (KBr):
n
¼3072, 2956, 2918, 2849 (w), 1672 (s), 1590
4.6. General procedure D-1 for the synthesis of 7aef
(w), 1580 (m), 1494, 1436 (w), 1424 (s), 1395 (w), 1326 (s), 1298 (w),
1270, 1245 (s), 1213 (m), 1190, 1164 (w), 1128 (s), 1092 (m), 1037,
1014, 1002, 984 (w), 927, 901, 889, 835, 820, 801 (s), 767, 738, 727
(w), 713 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼467 ([M, 37Cl]þ, 54),
466 ([MꢂH, 37Cl]þ, 100), 465 ([M, 35Cl]þ, 95), 432 (12), 431 (51), 304
(25), 298 (36), 270 (70), 249 (20). HRMS (EI, 70 eV): calcd for C21H10
ClF3O5S [M, 35Cl]þ: 465.98841; found: 465.98696.
A 1,4-dioxane solution of 9,10-dioxo-9,10-dihydroanthracene-
1,3-diyl bis(trifluoromethanesulfonate) 4a (0.2 mmol), arylboronic
acid (1.0 equiv), K3PO4 (1.5 equiv) and Pd(PPh3)4 (3 mol %) was
heated at 60 ꢀC for 30 h under argon atmosphere. After cooling to
20 ꢀC, CH2Cl2 (20 mL) was added, the solution was filtered and the
filtrate was concentrated in vacuo. The residue was purified by
column chromatography (EtOAc/Heptanes).
4.6.4. 4-(4-Fluorophenyl)-9,10-dioxo-9,10-dihydroanthracen-2-yl
trifluoromethanesulfonate (7d). Starting with 4a (100 mg,
0.2 mmol), arylboronic acid (28 mg, 0.2 mmol), K3PO4 (64 mg,
0.3 mmol) and Pd(PPh3)4 (07 mg, 3 mol %), 7d was prepared as
a yellow solid (66 mg, 73%). Mp: 148e150 ꢀC; reaction temperature:
4.6.1. 4-(4-Methoxyphenyl)-9,10-dioxo-9,10-dihydroanthracen-2-yl
trifluoromethanesulfonate (7a). Starting with 4a (100 mg,
0.2 mmol), arylboronic acid (30 mg, 0.2 mmol), K3PO4 (64 mg,
0.3 mmol) and Pd(PPh3)4 (07 mg, 3 mol %), 7a was prepared as
a yellow solid (65 mg, 70%). Mp: 151e153 ꢀC; reaction temperature:
60 ꢀC for 30 h. 1H NMR (500 MHz, CDCl3):
d
¼7.08 (t, 2H, J¼8.8 Hz,
ArH), 7.17e7.21 (m, 2H, ArH), 7.38 (d, 1H, J¼2.8 Hz, ArH), 7.67e7.74
60 ꢀC for 30 h. 1H NMR (300 MHz, CDCl3):
d
¼3.82 (s, 3H, OCH3), 6.94
(m, 2H, ArH), 8.02e8.08 (m, 1H, ArH), 8.19e8.22 (m, 2H, ArH). 19
F
(d, 2H, J¼8.7 Hz, ArH), 7.15e7.20 (m, 2H, ArH), 7.41 (d, 1H, J¼2.6 Hz,
ArH), 7.69e7.76 (m, 2H, ArH), 8.05e8.10 (m, 1H, ArH), 8.18 (d, 1H,
J¼2.8 Hz, ArH), 8.20e8.26 (m, 1H, ArH). 19F NMR (282.4 MHz,
NMR (282.4 MHz, CDCl3):
CDCl3):
127.1, 127.6 (CH), 129.7 (d, JC,F¼8.2 Hz, CH), 129.9 (CH), 130.6, 132.4
(C), 134.2 (CH), 134.3 (C), 134.9 (CH), 135.8 (d, JC,F¼3.7 Hz, C), 137.4,
146.9, 151.6 (C), 162.7 (d, JC,F¼248.4 Hz, CF), 181.4, 181.9 (CO). IR
d
¼ꢂ113.5, ꢂ72.6. 13C NMR (125.8 MHz,
d
¼115.4 (d, JC,F¼22.0 Hz, CH),118.4 (q, JC,F¼320.9, CF3),119.7,
CDCl3):
d
¼ꢂ72.4. 13C NMR (62.9 MHz, CDCl3):
¼55.3 (s, 3H, OCH3),
d
113.8 (CH), 118.7 (q, JC,F¼320.9, CF3), 119.2, 127.0, 127.6, 129.3, 130.1
(CH), 130.6, 132.0, 132.4 (C), 134.0 (CH), 134.5 (C), 134.8 (CH), 137.4,
(KBr):
n
¼3100, 3074, 2955, 2922, 2852 (w), 1672 (s), 1604, 1591,
147.8, 151.5, 159.6 (C), 181.6, 182.1 (CO). IR (KBr):
n
¼3066, 3012,
1578, 1511 (m), 1424, 1326 (s), 1298 (w), 1268, 1243, 1215 (s), 1187,
1157 (m), 1132, 1122 (s), 1039, 1037, 1014, 1004, 983, 965 (w), 926,
2965, 2919, 2849, 1732 (w), 1672 (s), 1607, 1590, 1580, 1512, 1463,
1455 (m), 1426, 1326 (s), 1305, 1290 (w), 1268 (m), 1244, 1212 (s),
1176 (m), 1129 (s), 1107, 1088, 1030, 1001 (m), 982 (w), 926, 900,
830, 820, 801 (s), 775 (w), 759, 740, 731 (m), 713 (s) cmꢂ1. GCeMS
(EI, 70 eV): m/z (%)¼462 ([M]þ, 91), 461 ([MꢂH]þ, 26), 431 (09), 330
(24), 329 (100), 301 (25), 286 (18), 273 (16), 258 (15), 230 (10).
901, 887, 835, 822 (s), 800, 786, 766, 739, 728 (m), 713 (s) cmꢂ1
.
GCeMS (EI, 70 eV): m/z (%)¼450 ([M]þ, 100), 318 (10), 317 (57), 289
(31), 288 (49), 261 (21), 233 (37), 231 (30). HRMS (EI, 70 eV):
calcd for C21H10F4O5S [M]þ: 450.01796; found: 4650.01712.
HRMS (ESI-TOF/MS, 70 eV): calcd for
463.04580; found: 463.04620.
C
22H14F3O6S [MþH]þ:
4.6.5. 4-(3,4-Dimethoxyphenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethanesulfonate (7e). Starting with 4a (100 mg,
0.2 mmol), arylboronic acid (36 mg, 0.2 mmol), K3PO4 (64 mg,
0.3 mmol) and Pd(PPh3)4 (07 mg, 3 mol %), 7e was prepared as
a yellow solid (80 mg, 81%). Mp: 169e171 ꢀC; reaction temperature:
4.6.2. 4-(3,5-Dimethylphenyl)-9,10-dioxo-9,10-dihydroanthracen-2yl
trifluoromethanesulfonate (7b). Starting with 4a (100 mg,
0.2 mmol), arylboronic acid (30 mg, 0.2 mmol), K3PO4 (64 mg,
0.3 mmol) and Pd(PPh3)4 (07 mg, 3 mol %), 7b was prepared as
a yellow solid (71 mg, 77%). Mp: 197e199 ꢀC; reaction temperature:
60 ꢀC for 30 h. 1H NMR (300 MHz, CDCl3):
d
¼3.81 (s, 3H, OCH3), 3.90
(s, 3H, OCH3), 6.74 (br d, 1H, J¼2.1 Hz, ArH), 6.80 (dd, 1H, J¼8.3,
2.1 Hz, ArH), 6.91 (br d, 1H, J¼8.2 Hz, ArH), 7.44 (d, 1H, J¼2.8 Hz,
ArH), 7.70e7.76 (m, 2H, ArH), 8.05e8.10 (m, 1H, ArH), 8.18 (d, 1H,
J¼2.6 Hz, ArH), 8.21e8.26 (m, 1H, ArH) 19F NMR (282.4 MHz,
60 ꢀC for 30 h. 1H NMR (300 MHz, CDCl3):
d
¼2.31 (s, 6H, 2CH3), 6.83
(br s, 2H, ArH), 7.03 (br s, 1H, ArH), 7.40 (d, 1H, J¼2.6 Hz, ArH),
7.68e7.74 (m, 2H, ArH), 8.04e8.09 (m, 1H, ArH), 8.17 (d, 1H,
J¼2.6 Hz, ArH), 8.19e8.25 (m, 1H, ArH). 19F NMR (282.4 MHz,
CDCl3):
d
¼ꢂ72.6. 13C NMR (62.9 MHz, CDCl3):
¼55.9, 56.0 (OCH3),
d
109.2, 109.9 (CH), 117.0 (q, JC,F¼320.9, CF3), 117.6 (C), 118.7, 119.5
(CH), 125.4, 125.9 (C), 128.4, 128.9, 130.7, 132.4, 132.8 (CH), 133.2,
135.7, 146.1, 147.1, 147.4, 149.8 (C), 179.5, 180.3 (CO). IR (KBr):
CDCl3):
d
¼ꢂ72.7. 13C NMR (62.9 MHz, CDCl3):
¼21.4 (s, 6H, 2CH3),
d
113.8 (CH), 118.7 (q, JC,F¼320.9, CF3), 119.3, 125.5, 127.0, 127.7, 129.7,
129.8 (CH), 132.0, 132.4 (C), 134.0 (CH), 134.4 (C), 134.8 (CH), 137.3,
n
¼3105, 3075, 3064, 3008, 2968, 2938, 2913, 2836 (w), 1681, 1674
137.9, 139.9, 148.4, 151.5 (C), 181.6, 181.9 (CO). IR (KBr):
n
¼3108,
(s), 1590, 1574, 1509 (m), 1464 (w), 1455, 1442, 1429, 1327, 1287,
1276, 1244 (m), 1204 (s), 1171, 1158 (w), 1139, 1119 (s), 1037 (w),
1027, 1008 (s), 978 (w), 865 (s), 833, 825, 814, 798, 779, 767, 757,
730, 711 (w) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼492 ([M]þ, 50), 477
(12), 461 (21), 331 (08), 328 (10), 300 (32), 281 (08), 273 (08), 207
3067, 3009, 2953, 2919, 2853 (w), 1673 (s), 1593, 1573, 1433, 1424,
1402 (m), 1385 (w), 1334 (m), 1312 (w), 1275, 1249 (m), 1204 (s),
1155 (w), 1143, 1130 (s), 1101, 1042, 1016, 998, 978 (w), 918, 893
(m), 858, 850, 818 (s), 793, 768 (w), 730, 713 (m), 705 (s) cmꢂ1
.

9022
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
(100). HRMS (EI, 70 eV): calcd for C23H15F3O7S [M]þ: 492.04851;
found: 492.04908.
1248 (m), 1211 (s), 1167, 1157, 1041, 1019, 1009, 966, 937, 916, 908,
902 (w), 869, 847 (m), 817, 795 (s), 768, 754, 712 (w), 710 (s) cmꢂ1
.
GCeMS (EI, 70 eV): m/z (%)¼496 ([M, 37Cl]þ, 12), 494 ([M, 35Cl]þ,
12), 363 (15), 365 (32), 361 (38), 349 (12), 347 (35), 239 (07), 226
(07), 191 (10), 57 (100). HRMS (EI, 70 eV): calcd for C23H14ClF3O5S
[M, 35Cl]þ: 494.01971; found: 494.02152.
4.6.6. 4-(3-Chlorophenyl)-9,10-dioxo-9,10-dihydroanthracen-2-yl
trifluoromethanesulfonate (7f). Starting with 4a (100 mg,
0.2 mmol), 7f was prepared as a yellow solid (63 mg, 68%). Mp:
134e136 ꢀC; reaction temperature: 60 ꢀC for 30 h. 1H NMR
(300 MHz, CDCl3):
d
¼7.11 (dt, 1H, J¼7.1, 1.7 Hz, ArH), 7.21e7.22 (m,
4.7.3. 3-Chloro-4-(4-chlorophenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethanesulfonate (7i). Starting with 4b (70 mg,
0.13 mmol), arylboronic acid (21 mg, 0.13 mmol), K3PO4 (41 mg,
0.2 mmol) and Pd(PPh3)4 (05 mg, 3 mol %), 7i was prepared as
a yellow solid (44 mg, 68%). Mp: 191e193 ꢀC; reaction temperature:
1H, ArH), 7.31e7.39 (m, 3H, ArH), 7.69e7.77 (m, 2H, ArH), 8.02e8.08
(m, 1H, ArH), 8.19e8.26 (m, 2H, ArH). 13C NMR (62.9 MHz, CDCl3):
d
¼117.7 (q, JC,F¼320.3, CF3), 120.0, 126.1, 127.2, 127.7, 127.9, 128.2,
129.6, 129.7 (CH), 130.5, 132.3, 134.1, 134.2 (C), 134.3, 135.0 (CH),
137.4, 141.6, 146.2, 151.6 (C), 181.3, 181.7 (CO). IR (KBr):
¼3072,
n
70 ꢀC for 18 h. 1H NMR (300 MHz, CDCl3):
d
¼7.04 (d, 2H, J¼8.5 Hz,
2917, 2849 (w), 1672 (s), 1577, 1567, 1478, 1423, 1320 (m), 1297 (w),
1271, 1244 (m), 1210 (s), 1164 (w), 1134 (s), 1101, 1086, 1078 (m),
1037, 1002, 979 (w), 931 (s), 911, 879, 845, 827, 816, 801, 785 (m),
767, 741 (w), 724, 708 (m) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼468
([M, 37Cl]þ, 36), 466 ([M, 35Cl]þ, 99), 431 (89), 298 (33), 270 (100),
213 (62). HRMS (EI, 70 eV): calcd for C21H10ClO5F3S [M, 35Cl]þ:
465.98841; found: 465.987174.
ArH), 7.44 (d, 2H, J¼8.5 Hz, ArH), 7.68e7.77 (m, 2H, ArH), 7.98e8.04
(m, 1H, ArH), 8.19e8.25 (m, 1H, ArH), 8.33 (s, 1H, ArH). 19F NMR
(282.4 MHz, CDCl3):
d
¼ꢂ73.0. 13C NMR (62.9 MHz, CDCl3):
¼118.7
d
(q, JC,F¼320.4, CF3), 121.1, 127.1, 127.8, 129.0, 129.2 (CH), 132.1, 134.0,
134.3 (C), 134.4 (CH), 134.5, 134.8 (C), 135.0 (CH), 135.4, 135.7, 144.3,
149.0 (C), 180.8, 181.2 (CO). IR (KBr):
n
¼3080, 2920, 2851 (w), 1677
(s), 1588, 1563 (m), 1490 (w), 1436 (s), 1417, 1400 (w), 1328, 1317,
1294 (s), 1276 (w), 1256, 1242, 1210 (s), 1179, 1163 (w), 1133 (s),
1024, 1016 (m), 969, 946 (w), 899 (s), 842 (w), 829, 802, 765,
758 (m), 732, 725 (s), 710, 703 (w) cmꢂ1. GCeMS (EI, 70 eV): m/z
(%)¼502 ([M, 37Cl]þ, 45), 500 ([M, 35Cl]þ, 65), 465 (12), 370 (20), 369
(66), 367 (100), 332 (19), 306 (12), 304 (37), 213 (27). HRMS (EI,
70 eV): calcd for C21H9Cl2F3O5S [M, 37Cl]þ: 501.94649; found:
501.94737; calcd for C21H9Cl2F3O5S [M, 35Cl]þ: 499.94944: found:
499.95015.
4.7. General procedure D-2 for the synthesis of 7gek
A 1,4-dioxane solution of 4b (0.13 mmol), arylboronic acid
(1.0 equiv), K3PO4 (1.5 equiv) and Pd(PPh3)4 (3 mol %) was heated at
70 ꢀC for 18 h under argon atmosphere. After cooling to 20 ꢀC,
CH2Cl2 (20 mL) was added, the solution was filtered and the filtrate
was concentrated in vacuo. The residue was purified by column
chromatography (EtOAc/Heptanes).
4.7.4. 3-Chloro-4-(4-ethoxyphenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethanesulfonate (7j). Starting with 4b (70 mg,
0.13 mmol), arylboronic acid (22 mg, 0.13 mmol), K3PO4 (41 mg,
0.2 mmol) and Pd(PPh3)4 (05 mg, 3 mol %), 7j was prepared as
a yellow solid (54 mg, 81%). Mp: 153e155 ꢀC; reaction temperature:
4.7.1. 3-Chloro-4-(4-methoxyphenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethane-sulfonate (7g). Starting with 4b (70 mg,
0.13 mmol), arylboronic acid (30 mg, 0.13 mmol), K3PO4 (64 mg,
0.2 mmol) and Pd(PPh3)4 (05 mg, 3 mol %), 7g was prepared as an
orange solid (56 mg, 86%). Mp: 193e195 ꢀC; reaction temperature:
70 ꢀC for 18 h. 1H NMR (300 MHz, CDCl3):
d
¼1.40 (t, 3H, J¼7.0 Hz,
70 ꢀC for 18 h. 1H NMR (300 MHz, CDCl3):
d
¼3.83 (s, 3H, OCH3),
CH3), 4.06 (q, 2H, J¼7.0 Hz, OCH2), 6.94e7.02 (m, 4H, ArH),
7.66e7.79 (m, 2H, ArH), 7.99e8.06 (m, 1H, ArH), 8.18e8.24 (m, 1H,
6.97e7.02 (m, 4H, ArH), 7.67e7.74 (m, 2H, ArH), 8.00e8.03 (m, 1H,
ArH), 8.19e8.22 (m,1H, ArH), 8.30 (s,1H, ArH). 19F NMR (282.4 MHz,
ArH), 8.33 (s, 1H, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ73.1. 13
C
CDCl3):
d
¼ꢂ73.1. 13C NMR (75.5 MHz, CDCl3):
d
¼55.2 (s, 3H, OCH3),
NMR (62.9 MHz, CDCl3):
d
¼14.9 (CH3), 63.4 (OCH2), 114.5 (CH),
114.1 (CH), 118.6 (q, JC,F¼320.8, CF3), 120.1, 127.0, 127.8, 129.1 (CH),
118.9 (q, JC,F¼320.9, CF3), 120.8, 127.0, 127.8, 129.0 (CH), 129.1, 130.7,
131.8, 132.1, 132.2 (C), 134.2 (CH), 134.3, 134.4 (C), 134.9 (CH), 135.9,
132.1 (C), 134.2 (CH), 134.3, 134.4 (C), 134.9 (CH), 135.6, 145.6, 148.8,
145.6, 148.9, 159.5 (C), 181.1, 182.4 (CO). IR (KBr):
n
¼3080, 3014,
158.9 (C), 181.1, 181.3 (CO). IR (KBr):
n
¼3077, 3042, 2985, 2852 (w),
2979, 2900, 2841 (w), 1678 (m), 1607, 1566, 1514, 1462, 1440 (w),
1427 (s), 1409 (w), 1329 (m),1309 (w),1290 (m),1249,1218 (s),1177,
1768 (m), 1133 (s), 1112, 1093, 1043 (w), 1021 (m), 977, 969, 944 (w),
917 (m), 901 (s), 847 (w), 829, 811, 799 (s), 766 (w), 759, 753 (m),
716 (s), 707 (w) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼498 ([M, 37Cl]þ,
31), 496 ([M, 35Cl]þ, 69), 365 (32), 363 (100), 320 (30), 300 (11), 285
(18), 273 (10), 257 (15). HRMS (EI, 70 eV): calcd for C22H12ClF3O6S
[M, 37Cl]þ: 497.99602; found: 497.99437; calcd for C22H12ClF3O6S
[M, 35Cl]þ: 495.99897; found: 495.99908.
1677 (s), 1608 (m), 1583, 1564, 1538 (w), 1514 (m), 1478, 1456 (w),
1429 (s), 1416, 1393 (w), 1329 (m), 1310 (w), 1294, 1288 (m), 1270
(w), 1243, 1212, 1201 (s), 1180, 1163 (w), 1138, 1115, 1042, 1018 (m),
979, 968, 945, 910 (w), 856 (m), 808, 801 (s), 761, 754 (m), 713 (s),
702 (w) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼512 ([M, 37Cl]þ, 34), 510
([M, 35Cl]þ, 100) 481 (04), 379 (14), 377 (44), 351 (26), 349 (91), 286
(15), 257 (06). HRMS (EI, 70 eV): calcd for C23H14ClF3O6S [M, 37Cl]þ:
512.01167; found: 512.01432; calcd for C23H14ClF3O6S [M, 35Cl]þ:
510.01432: found: 510.01462.
4.7.2. 3-Chloro-4-(3,5-dimethylphenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethanesulfonate (7h). Starting with 4b (70 mg,
0.13 mmol), arylboronic acid (20 mg, 0.13 mmol), K3PO4 (41 mg,
0.2 mmol) and Pd(PPh3)4 (05 mg, 3 mol %), 7h was prepared as
a yellow solid (48 mg, 75%). Mp: 192e194 ꢀC; reaction temperature:
4.7.5. 3-Chloro-4-(3-nitrophenyl)-9,10-dioxo-9,10-dihydroanthracen-
2-yl trifluoromethanesulfonate (7k). Starting with 4b (70 mg,
0.13 mmol), arylboronic acid (22 mg, 0.13 mmol), K3PO4 (41 mg,
0.2 mmol) and Pd(PPh3)4 (5 mg, 3 mol %), 7k was prepared as
a yellow solid (42 mg, 63%). Mp: 161e163 ꢀC; reaction temperature:
70 ꢀC for 18 h. 1H NMR (500 MHz, CDCl3): 7.46 (dt, 1H, J¼7.6, 1.4 Hz,
ArH), 7.66 (br t, 1H, J¼8.0 Hz, ArH), 7.71e7.74 (m, 1H, ArH),
7.75e7.78 (m, 1H, ArH), 7.97 (dd, 1H, J¼7.6, 1.3 Hz, ArH), 7.99e8.01
(m, 1H, ArH), 8.24 (dd, 1H, J¼7.4, 1.1 Hz, ArH), 8.32 (ddd, 1H, J¼8.2,
2.2, 0.9 Hz, ArH), 8.39 (s, 1H, ArH). 19F NMR (282.4 MHz, CDCl3):
70 ꢀC for 18 h. 1H NMR (300 MHz, CDCl3):
d
¼2.32 (s, 6H, 2CH3), 6.70
(br s, 2H, ArH), 7.07 (br s, 1H, ArH), 7.67e7.75 (m, 2H, ArH),
8.00e8.05 (m, 1H, ArH), 8.17e8.23 (m, 1H, ArH), 8.30 (s, 1H, ArH).
19F NMR (282.4 MHz, CDCl3):
d
d
¼ꢂ73.1. 13C NMR (62.9 MHz, CDCl3):
¼20.2 (2CH3), 117.6 (q, JC,F¼320.4, CF3), 119.7, 124.3, 126.0, 126.9,
128.9 (CH), 130.5, 131.1 (C), 133.2 (CH), 133.3, 133.4 (C), 133.9 (CH),
134.5, 136.2, 137.1, 145.1, 147.8 (C), 180.0, 180.1 (CO). IR (KBr):
d
¼ꢂ72.9. 13C NMR (62.9 MHz, CDCl3):
¼117.6 (q, JC,F¼320.8, CF3),
d
121.0, 122.1, 122.3, 126.3, 126.8, 128.7 (CH), 130.4, 131.1, 132.7 (C),
133.1 (CH), 133.6 (C), 133.7 (CH), 134.1 (C), 134.2 (CH), 137.8, 141.6,
n
¼3100, 3084, 3041, 2957, 2921, 2853, 2737 (w), 1673 (s), 1588,1564
(m), 1495, 1479, 1456 (w), 1432 (s), 1377, 1362 (w), 1334, 1292, 1262,
147.5, 148.1 (C), 179.5, 180.1 (CO). IR (KBr):
n¼3094, 3079, 2954,

O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
9023
2919, 2851 (w), 1737 (m), 1674 (s), 1615, 1591, 1567 (w), 1529 (s),
1482 (w), 1435 (s), 1375 (w), 1347, 1329, 1294 (m), 1282, 1274 (w),
1252, 1242, 1213 (s), 1168, 1162 (w), 1131 (s), 1093, 1079, 1042, 1024,
973, 925, 908, 898 (w), 874 (s), 829 (m), 800 (s), 765, 756, 745, 717
(w), 708 (s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼513 ([M, 37Cl]þ, 42),
511 ([M, 35Cl]þ, 100), 496 (14), 494 (34), 481 (20), 464 (17), 446 (16),
401 (12), 380 (21), 378 (47), 348 (63), 332 (53), 306 (18), 304 (50),
276 (11), 247 (08). HRMS (EI, 70 eV): calcd for C21H9ClF3NO7S
[M, 37Cl]þ: 512.97054; found: 512.97186; calcd for C21H9ClF3NO7S
[M, 35Cl]þ: 510.97349: found: 510.97376.
m/z (%)¼410 ([M, 37Cl]þ, 21), 408 ([M, 35Cl]þ, 58), 407 ([MꢂH, 35Cl]þ,
100), 373 (27). HRMS (EI, 70 eV): calcd for C27H16O2Cl [MꢂH, 35Cl]þ:
407.08333; found: 407.082634.
4.9. General procedure E-2 for the synthesis of 8c,d
A 1,4-dioxane solution of 4b (0.2 mmol), Ar1B(OH)2 (1.0 equiv),
K3PO4 (1.5 equiv) and Pd(PPh3)4 (3 mol %) was heated at 70 ꢀC for
18 h under argon atmosphere. After cooling to 20 ꢀC, Ar2B(OH)2
(1.3 equiv) and Pd(PPh3)4 (3 mol %) were added and the reaction
mixture was heated at 115 ꢀC for further 12 h. The reaction mixture
was cooled again to 20 ꢀC, H2O was added and the reaction mixture
was extracted with CH2Cl2 (25ꢁ3 mL). The organic layers were
dried (Na2SO4), filtered and the filtrate was concentrated in vacuo.
The residue was purified by column chromatography (EtOAc/
Heptanes).
4.8. General procedure E-1 for the synthesis of 8a,b
A 1,4-dioxane solution of 4a (0.3 mmol), Ar1B(OH)2 (1.0 equiv),
K3PO4 (3.0 equiv) and Pd(PPh3)4 (3 mol %) was heated at 60 ꢀC for
30 h under argon atmosphere. After cooling to 20 ꢀC, Ar2B(OH)2
(1.2 equiv) and Pd(PPh3)4 (3 mol %) were added and the reaction
mixture was heated at 100 ꢀC for further 5 h. The reaction mixture
was cooled again to 20 ꢀC, H2O was added and the reaction mixture
was extracted with CH2Cl2 (25ꢁ3 mL). The organic layers were
dried (Na2SO4), filtered and the filtrate was concentrated in vacuo.
The residue was purified by column chromatography (EtOAc/
Heptanes).
4.9.1. 2-Chloro-1-(4-chlorophenyl)-3-(4-methoxyphenyl)anthracene-
9,10-dione (8c). Starting with 4b (108 mg, 0.2 mmol),
4-chlorophenylboronic acid as Ar1B(OH)2 (31 mg, 0.20 mmol),
K3PO4 (64 mg, 0.3 mmol), Pd(PPh3)4 (07 mg,
3 mol %),
4-methoxyphenylboronic acid as Ar2B(OH)2 (40 mg, 0.26 mmol),
K3PO4 (64 mg, 0.3 mmol) and Pd(PPh3)4 (09 mg, 4 mol-%), 8c was
prepared according to general procedure E-2 as a yellow solid
(72 mg, 78%). Mp: 187e189 ꢀC; reaction temperature: was 70 ꢀC for
4.8.1. 3-(4-(tert-Butyl)phenyl)-1-(4-methoxyphenyl)anthracene-
9,10-dione (8a). Starting with 4a (150 mg, 0.3 mmol), 4-
methoxyphenylboronic acid as Ar1B(OH)2 (46 mg, 0.30 mmol),
K3PO4 (191 mg, 0.9 mmol), Pd(PPh3)4 (21 mg, 6 mol %) and p-(tert-
butyl)phenyl boronic acid as Ar2B(OH)2 (53 mg, 0.30 mmol), 8a was
prepared according to the general procedure E-1 as a yellow solid
(99 mg, 74%). Mp: 228e230 ꢀC; reaction temperature: 60 ꢀC for 30 h
18 h and 115 ꢀC for 12 h. 1H NMR (300 MHz, CDCl3):
d
¼3.81 (s, 3H,
OCH3), 6.95 (d, 2H, J¼8.9 Hz, ArH), 7.23 (d, 2H, J¼8.5 Hz, ArH),
7.36e7.44 (m, 6H, ArH), 8.01e8.04 (m, 1H, ArH), 8.19e8.22 (m, 1H,
ArH), 8.34 (s, 1H, ArH). 13C NMR (75.5. MHz, CDCl3):
112.8, 125.8, 126.5, 127.7, 128.4, 129.1 (CH), 129.4 (C), 129.7 (CH),
131.6, 131.7, 132.4 (C), 132.9 (CH), 133.4 (C), 133.5 (CH), 136.9, 139.5,
d
¼54.3 (OCH3),
and 100 ꢀC for 5 h. 1H NMR (300 MHz, CDCl3):
d¼1.34 (s, 9H,
140.9, 145.3, 159.0 (C), 181.3, 181.7 (CO). IR (KBr):
n
¼3051, 3002,
C(CH3)3), 3.79 (s, 3H, OCH3), 6.93 (d, 2H, J¼8.9 Hz, ArH), 7.23 (d, 2H,
J¼8.3 Hz, ArH), 7.42 (d, 2H, J¼8.3 Hz, ArH), 7.61e7.68 (m, 4H, ArH),
7.71 (d, 1H, J¼2.1 Hz, ArH), 8.06e8.11 (m, 1H, ArH), 8.19e8.26 (m,
1H, ArH), 8.56 (d, 1H, J¼2.1 Hz, ArH). 13C NMR (75.5. MHz, CDCl3):
2958, 2920, 2850, 1738, 1731 (w), 1670 (s), 1605, 1589 (w), 1569,
1511 (m), 1487, 1462, 1455, 1417, 1396, 1377 (w), 1339, 1293, 1274
(m),1256, 1247 (s), 1172 (m), 1112 (w), 1086, 1027, 1013 (m), 977 (w),
962 (m), 939, 923, 849 (w), 820, 800, 782 (s), 763, 736, 727 (w), 713
(s), 701 (m) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼462 ([M, 37Cl, 37Cl]þ,
14), 460 ([M, 35Cl, 37Cl]þ, 66), 458 ([M, 35Cl, 35Cl]þ, 100), 425 (25),
423 (57), 414 (14), 380 (20), 344 (07), 323 (06), 289 (13), 287 (20).
HRMS (EI, 70 eV): calcd for C27H16Cl2O3 [M, 37Cl, 37Cl]þ: 462.04120;
d
¼30.4 (3CH3), 33.6 (C), 54.4 (OCH3),113.5,123.5,124.0,125.7,126.4,
126.9, 127.5 (CH), 127.8, 129.8, 131.9 (C), 132.5, 133.2 (CH), 133.8,
134.4 (C),134.6 (CH),138.2,143.8,144.3,149.0,159.5 (C),182.0,182.6
(CO). IR (KBr):
n
¼3066, 2956, 2922, 2853, 1737 (w), 1667 (s), 1633
(w), 1588, 1579 (s), 1557, 1539 (w), 1519 (s), 1494, 1454, 1434, 1398,
1361 (w), 1341, 1304, 1293 (s), 1264 (m), 1227, 1194 (w), 1183, 1164
(s), 1115 (w), 1080 (m), 1063 (w) 1025, 1017 (s), 963 (m), 924, 896,
872, 848 (w), 828, 819, 798 (s), 775, 750, 739, 724 (w), 710, 704
(s) cmꢂ1. GCeMS (EI, 70 eV): m/z (%)¼446 ([M]þ, 41), 431 (60), 390
(29), 389 (100), 346 (07). HRMS (EI, 70 eV): calcd for C31H26O3 [M]þ:
446.18765; found: 446.18665.
found: 462.04255; calcd for C
27H16Cl2O3 [M, 35Cl, 37Cl]þ:
460.04415; found: 460.04396; calcd for C27H16Cl2O3 [M, 35Cl,
35Cl]þ: 458.04710; found: 458.04650.
4.9.2. 2-Chloro-1-(4-fluorophenyl)-3-(4-methoxyphenyl) anthracene-
9,10-dione (8d). Starting with 4b (108 mg, 0.2 mmol),
4-fluorophenylboronic acid as Ar1B(OH)2 (28 mg, 0.20 mmol),
K3PO4 (64 mg, 0.3 mmol), Pd(PPh3)4 (07 mg, 3 mol %), 4-methox-
yphenylboronic acid as Ar2B(OH)2 (40 mg, 0.26 mmol), K3PO4
(64 mg, 0.3 mmol) and Pd(PPh3)4 (9 mg, 4 mol-%), 8d was prepared
according to general procedure E-2 as a yellow solid (60 mg, 68%).
Mp: 220e222. Reaction temperature: 70 ꢀC for 18 h and 115 ꢀC for
4.8.2. 1-(3-Chlorophenyl)-3-p-tolylanthracene-9,10-dione
(8b). Starting with 4a (150 mg, 0.3 mmol), 3-chlorophenylboronic
acid as Ar1B(OH)2 (47 mg, 0.30 mmol), K3PO4 (191 mg, 0.9 mmol),
Pd(PPh3)4 (21 mg, 6 mol %) and p-tolylboronic acid as Ar2B(OH)2
(49 mg, 0.30 mmol), 8b was prepared according to general pro-
cedure E-1 as a yellow solid (80 mg, 65%). Mp: 191e193 ꢀC; reaction
temperature: was 60 ꢀC for 30 h and 100 ꢀC for 5 h. 1H NMR
12 h. 1H NMR (300 MHz, CDCl3):
d
¼3.81 (s, 3H, OCH3), 6.94 (d, 2H,
J¼8.9 Hz, ArH), 7.07e7.16 (m, 4H, ArH), 7.41 (d, 2H, J¼8.7 Hz, ArH),
7.63e7.72 (m, 2H, ArH), 7.98e8.04 (m, 1H, ArH), 8.17e8.23 (m, 1H,
(300 MHz, CDCl3):
d
¼2.33 (s, 3H, CH3), 7.12e7.33 (m, 6H, ArH), 7.55
ArH), 8.33 (s, 1H, ArH). 19F NMR (282.4 MHz, CDCl3):
d
¼ꢂ114.4. 13
C
(d, 2H, J¼8.1 Hz, ArH), 7.65e7.68 (m, 3H, ArH), 8.03e8.06 (m, 1H,
NMR (75.5.MHz, CDCl3):
d
¼55.4 (OCH3), 113.8 (CH), 115.6 (d,
ArH), 8.20e8.23 (m, 1H, ArH), 8.54 (d, 1H, J¼1.9 Hz, ArH). 13C NMR
JC,F¼21.5 Hz, CH), 126.8, 127.6 (CH), 129.8 (d, JC,F¼8.3 Hz, CH), 130.0
(CH), 130.5 (C), 130.7 (CH), 130.8, 132.5, 132.6 (C), 133.9, 134.4 (CH),
134.5 (C), 135.3 (d, JC,F¼3.9 Hz, C), 140.8, 142.1, 146.2, 160.0 (C), 162.2
(62.9 MHz, CDCl3):
d
¼21.2 (CH3), 125.5, 126.4, 126.9, 127.1, 127.2,
127.4, 128.1 (CH), 129.1 (C), 129.3, 129.9 (CH), 132.9 (C), 133.7 (CH),
133.9 (C), 134.3 (CH), 134.5 (C), 135.2 (CH), 135.3, 139.3, 143.5, 143.9,
(d, JC,F¼245.9 Hz, CF), 182.4, 182.8 (CO). IR (KBr): ¼3105, 3076,
n
145.5 (C), 182.8, 183.3 (CO). IR (KBr):
n
¼3063, 3034, 2950, 2915,
3050, 2954, 2932, 2841, 1894 (w), 1668 (s), 1652, 1634, 1622 (m),
1604, 1590, 1569, 1543, 1539 (w), 1505 (s), 1462, 1454, 1443, 1413,
1403, 1377, 1361 (w), 1337 (s), 1292, 1277, 1252, 1246 (m), 1215 (s),
1110, 1059, 1090, 1030 (m), 1011, 979 (w), 963 (m), 947, 939, 932,
2852 (w), 1667 (s), 1613 (w), 1587, 1564, 1557 (m), 1537, 1518, 1504,
1476, 1445, 1408, 1386 (w), 1337, 1304, 1294, 1269, 1226, 1194, 1188,
1168 (m), 1153, 1077, 1061, 1034, 1018, 998 (w), 966, 930, 917, 901,
865, 853, 814, 785, 738 (m), 714, 713 (s) cmꢂ1. GCeMS (EI, 70 eV):
904, 848 (w), 833 (s), 818, 796 (m), 764, 739 (w), 712 (s) cmꢂ1
.

9024
O.A. Akrawi et al. / Tetrahedron 69 (2013) 9013e9024
GCeMS (EI, 70 eV): m/z (%)¼444 ([M, 37Cl]þ, 35), 442 ([M, 35Cl]þ,
100), 441 ([MꢂH, 35Cl]þ, 90), 423 (06), 398 (10), 364 (05), 335 (05),
307 (11). HRMS (EI, 70 eV): calcd for C27H16ClFO3 [M, 35Cl]þ:
442.07665; found: 442.07540.
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Financial support by the DAAD (scholarships for O.A.A. and for
A.K.) is gratefully acknowledged. The project is implemented
through the New Hungary Development Plan, co-financed by the
European Social Fund and the European Regional Development
Fund. The project was also funded by the EFRE program of the EU.
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