Optimized palladium(0)-catalyzed Suzuki cross-coupling reaction of polystyrene-supported selenenyl flavanones: A convenient preparation of biaryl-chromen-4-one

Article abstract of DOI:10.1002/cjoc.201280023

Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen-4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids with the resin-bound bromoflavanones whic

Full text of DOI:10.1002/cjoc.201280023

FULL PAPER
DOI: 10.1002/cjoc.201280023
Optimized Palladium(0)-catalyzed Suzuki Cross-coupling
Reaction of Polystyrene-supported Selenenyl Flavanones: A
Convenient Preparation of Biaryl-chromen-4-one
Tang, E*,a,b(汤峨)
Li, Wenb(李文)
Gao, Zhangyongb(高占勇)
Ma, Qiushib(马秋石)
Zhang, Lianpengb(张莲蓬)
a Key Laboratory of Medicinal Chemistry of Natural Resource (Yunnan University), Ministry of Education,
Kunming, Yunnan 650091, China
b Department of Applied Chemistry, Yunnan University, Kunming, Yunnan 650091, China
Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen-
4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids with the
resin-bound bromoflavanones which were prepared by organoselenium-induced regioselective intramolecular cy-
clization of bromo-2-hydroxylchalcones proceeded smoothly. Biaryl-chromen-4-ones were synthesized by subse-
quent selenoxide syn-elimination in good total yields.
Keywords biaryl-chromen-4-ones, Suzuki coupling, solid-phase synthesis, palladium(0), selenium
palladium(0) catalyst system and biarylchromen-4-
ones have been synthesized efficiently with good yields
by subsequent oxidative cleavage of selenium resins.
Introduction
Flavonoids are widely spread in the plant kingdom.[1]
Many flavonoids with biaryl configuration have been
reported to display a variety of biochemical properties
including spasmolytic,[2] antiarthritic,[3] and antiviral[4,5]
activities, reduction of histamine expression,[6] phos-
pholipase[7] and phosphodiesterase inhibition,[8] and
antimalarial[4,5,9] activities. In many cases, Such flavon-
oids exhibited more pronounced bioactivities.[4,5,10,11]
However, there are only a few reports on the synthesis
of flavonoids with biaryl configuration.[12] The Ullmann
coupling reaction[13] and the intramolecular oxidative
coupling technique[14] comprise major routes to the fla-
vonoids. Park[15] and Deodhar et al.[16] have reported the
synthesis of biflavonoids by Stille coupling reaction and
Suzuki coupling reaction. Caddick et al. have reported a
microwave enhanced diversity-oriented synthesis of
functionalized flavones using POPd as the catalyst.[17]
We have previously reported a simple solid-phase Su-
zuki cross-coupling reaction of arylboronic acid with
the resin-bounded 4'-bromo-flavanone employing a pal-
ladium dichloride catalyst system.[18] The Suzuki
cross-coupling reaction worked smoothly for most
arylboronic acids. However, the Suzuki coupling reac-
tion was incomplete when R (in RB(OH)2) is an aryl
group with a strong electron-withdrawing group such as
trifluoromethyl. Herein, we want to report an improved
Suzuki coupling reaction on polymer support using a
Results and Discussion
The solid-phase cyclization of 4'-bromo-2-hydroxyl-
chalcones (1a) with polystyrene-supported selenenyl
bromide (dark-red resin; Br, 0.99 mmol/g) in the pres-
ence of 40 mol% ZnCl2 was performed at room tem-
perature to afford resin 2a. A range of Suzuki coupling
cyclization reaction conditions involving Pd-catalysts,
solvents, bases and reaction time were explored while
phenylboronic acids (3.0 mmol) and resin 2a (0.5 g)
were used (Table 1).
In the first attempt, according to the report of the lit-
erature,[18] in the presence of K2CO3 and catalyzed by
0.3 mol% PdCl2, phenylboronic acids reacted smoothly
with resin 2a in pyridine, followed by selenoxide
syn-elimination to afford 4a.[18] The yield of 4a dropped
to 46% when the coupling reaction time extended to 24
h (Table 1, Entry 1). No product was gotten when the
coupling reaction was catalyzed by 1.0 mol% Pd(OAc)2
and carried out in CH3OH because of the low swelling
property of polystyrene in CH3OH (Table 2, Entry 4).
Cross-coupling reactions were performed in DMF or
DME with K3PO4 or Na2CO3, with different catalysts
such as PdCl2(PPh3)2 and Pd(PPh3)4, the best results
were obtained with 5.0 mol% Pd(PPh3)4 and Na2CO3 in
*
E-mail: tange@ynu.edu.cn; Fax: ＋86(871)5033725; Tel.: ＋86(871)5139510
Received April 11, 2011; accepted October 27, 2011.
Chin. J. Chem. 2012, 30, 585—589
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
585

Tang et al.
FULL PAPER
Table 1 Optimization of solid-phase conditions of cyclization
OH
O
Br
Br
PhB(OH)2, Pd-catalyst
Base, Solvent, Reflux
SeBr, ZnCl2
CH2Cl2, r.t.
Se
O
O
1a
O
2a
O
O
30% H2O2
THF, 0 oC - r.t.
Se
O
3a
4a
Entry
Pd-catalyst
0.3 mol% PdCl2
Basea
Solvent
Reaction time/h
Yield of 4ab/%
1
2
K2CO3
Na2CO3
K3PO4
Pyridine
DMF
24
8
46
32
20
0
1.0 mol% PdCl2(PPh3)2
1.0 mol% PdCl2(PPh3)2
1.0 mol% Pd(OAc)2
1.0 mol% Pd(PPh3)4
3.0 mol% Pd(PPh3)4
5.0 mol% Pd(PPh3)4
8.0 mol% Pd(PPh3)4
5.0 mol% Pd(PPh3)4
5.0 mol% Pd(PPh3)4
5.0 mol% Pd(PPh3)4
3
DMF
8
4
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
K3PO4
CH3OH
DMF
24
24
24
24
24
24
24
48
5
40
44
52
44
57
45
56
6
DMF
7
DMF
8
DMF
9
DME
DME
DME
10
11
Na2CO3
a 2.0 mol/L aqueous solution of base (4.0 mmol) in degassed solvent (15 mL). b Isolated yield.
DME and 24-hour reflux time (isolated yield: 57%)
(Table 1, Entries 2, 3, 5—10). Longer coupling reaction
time (48 h) did not increase significantly the yield of 4a
(Table 1, Entry 11 ).
Experimental
General procedures
The melting points were uncorrected. 1H NMR (400
MHz) and 13C NMR (100 MHz) spectra were recorded
on a Bruker Avance 400 spectrometer in CDCl3 or
DMSO-d6 with TMS as the internal standard; IR spectra
were recorded on a Bruker Vector 22 spectrometer.
EIMS were run on an HP 5989B mass spectrometer.
Elemental analysis was run on Thermofinnigan Flash
EA 1112. HRMS were performed on an Agllent LC/Msd
TOF instrument.
In order to extend the result, polystyrene-supported
selenenyl bromide was treated with a sample of bromo-
2-hydroxylchalcones and ZnCl2 to afford intermediates
2. Suzuki cross coupling reactions of a range of arylbo-
ronic acids with resins 2 were carried out. The results
are displayed in Table 2. From the table, We found that
in the presence of Pd(PPh3)4 and Na2CO3, the Suzuki
coupling reaction worked well despite R (in RB(OH)2)
being an aryl group with an electron-donating group or
an electron-withdrawing group. Especially, cross cou-
pling of 3-trifluoromethyl-4-chlorophenyl boronic acid
with resin 2 resulted, after cleavage, in 2-(4'-chloro-3'-
trifluoro-methyl-biphenyl-4-yl)chromen-4-one (4g) in
good total isolated yield of 48% (Table 2, Entry 7).
Furthermore, good coupling results were also obtained
when 3'-bromo-2-hydroxylchalcone, 3-bromo-2-hy-
droxychalcone, 4-bromo-2-hydroxy chalcone, and
5-bromo-2-hydroxychalcone were used as substrates
(Table 2, Entries 9, 11—13). Suzuki coupling reaction
also worked well when resin 2 reacted with flavone
pinacolato boronate and two diflavones were obtained
in total isolated yields of 40% and 42% (Table 2, En-
tries 8 and 10). However, no product was obtained when
4-nitrophenylboronic acid and 2-nitrophenylboronic
acid reacted with resin 2a.
Typical procedure for the preparation of fla-
vanone-supported selenium resin 2
To a suspension of the swollen polystyrene-
supported selenenyl bromide (Br: 0.99 mmol/g, 1.0 g) in
dry CH2Cl2 (20 mL) was added ZnCl2 (40 mol%) at
room temperature. After stirring for 0.5 h, substituted
3-(4-bromophenyl)-1-(2-hydroxyphenyl)prop-2-en-1-
one (1) (3.0 mmol) was added, and stirring was contin-
ued for another 12 h. The resin 2 was collected by filtra-
tion, washed with H2O (20 mL×4), THF/H2O (V/V＝
3/1) (20 mL×2), THF (15 mL×2), MeOH (15 mL×2)
and CH2Cl2 (15 mL×2) and dried in vacuum.
Typical procedure for the preparation of biaryl-
chromen-4-ones (4)
Resin 2 (0.5 g) was swollen in anhydrous DME (15
586
www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 585—589

Optimized Palladium(0)-catalyzed Suzuki Cross-coupling Reaction
Table 2 Solid-phase synthesis of biaryl-chromen-4-ones (4)
OH
O
SeBr, ZnCl2
CH2Cl2, r.t.
RB(OH)2, Pd(PPh3)4
Na2CO3, DME
x
x
Se
x
x
O
O
1
X = H or Br
2
O
O
30% H2O2
R
R
THF, 0 oC - r.t.
Se
R
R
O
O
R = H or Ar
3
4
Product
(Yielda/%)
Product
(Yielda/%)
Entry
1
Substrate
R
Entry
9
Substrate
R
4a (57)
4i (51)
Br
OH
O
O
O
b
2
3
4
5
4b (44)
4c (58)
4d (65)
4e (51)
10
11
12
13
4jc (42)
OH
4k (52)
4l (49)
Br
H3C
O
Br
OH
H3CO
OH
O
Br
O
Br
OH
4m (44)
Cl
F
O
6
7
4f (46)
4g (48)
CH3
Cl
CF3
O
b
8
4hc (40)
O
a
b
c
Isolated yields; The substrate was flavone pinacolato boronate; NaOH was used as the base in stead of Na2CO3 in Suzuki coupling
reaction.
mL) and the system was flushed with nitrogen (30 min).
Pd(PPh3)4 (5 mol %) was added, the reaction mixture
was stirred (30 min) and treated with degassed Na2CO3
solution (2 mol/L, 8 equiv.) and stirred for 30 min. The
boronic acid (6 equiv.) was added, the reaction mixture
was flushed with nitrogen (15 min), heated to reflux for
24—36 h, cooled to room temperature, and treated with
aqueous saturated NH4Cl solution (10 mL) and further
Chin. J. Chem. 2012, 30, 585—589
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
587

Tang et al.
FULL PAPER
1
stirred for 10 min. The resin was removed by filtration
and the filtrate was washed successively with DME (15
mL×2), DME/H2O (V∶V＝1∶1) (15 mL×2), 0.3
mol/L HCI (15 mL×2), H2O (30 mL×2), DMF (15
mL×2), EtOAc (15 mL×2), EtOAc/MeOH (V∶V＝
1∶1) (15 mL×2), MeOH (15 mL×2) and dried in
vacuo (12 h) to afford resin 3a—3g, 3i, 3k—3m.
Resin 2 (0.5 g) was swollen in anhydrous DME (15
mL) and the system was flushed with nitrogen (30 min).
Pd(PPh3)4 (5 mol%) was added, the reaction mixture
was stirred for 30 min and treated with degassed NaOH
solution (6 mol/L, 12 equiv.) and stirred for 30 min. The
flavone pinacolato boronate (4 equiv.) was added, the
reaction mixture was flushed with nitrogen for 15 min
and stirred at 85 ℃ for 16 h, cooled to room tempera-
ture, and treated with aqueous saturated NH4Cl solution
(15 mL) and further stirred for 10 min. The resin was
removed by filtration and the filtrate was washed suc-
cessively with saturated NH4Cl solution (30 mL×2),
DME (15 mL×2), DME/H2O (V∶V ＝1 ∶1) (15
mL×2), 0.3 mol/L HCI (15 mL×2), H2O (30 mL×2),
DMF (15 mL×2), EtOAc (15 mL×2), EtOAc/MeOH
(V∶V＝1∶1) (15 mL×2), MeOH (15 mL×2) and
dried in vacuo (12 h) to afford resin 3h and 3j.
White solid, m.p. 140—142 ℃; H NMR (CDCl3, 400
MHz) δ: 8.25 (d, J＝8.0 Hz, 1H), 8.00 (d, J＝8.4 Hz,
2H), 7.74 (d, J＝8.4 Hz, 2H), 7.70 (t, J＝6.8 Hz, 1H),
7.59 (d, J＝8.4 Hz, 1H), 7.56 (d, J＝8.0 Hz, 2H), 7.43 (t,
J＝7.6 Hz, 1H), 7.29 (d, J＝7.6 Hz, 2H), 6.87 (s, 1H),
2.42 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ: 178.7,
163.4, 159.4, 156.5, 144.6, 134.0, 132.0, 130.0, 127.5,
127.2, 127.0, 126.0, 125.4, 123.0, 118.3, 112.3, 107.5,
21.3; MS (70 ev) m/z (%): 192 (100), 312 (M＋); IR
－
1
(neat) ν: 2923, 1638, 1461, 1371, 1043, 811, 775 cm .
Anal. calcd for C22H16O2: C 84.59, H 5.16; found C
84.65, H 5.10.
2-(4'-Methoxy-biphenyl-4-yl)-chromen-4-one (4d)
1
White solid, m.p. 154—156 ℃; H NMR (CDCl3, 400
MHz) δ: 8.25 (d, J＝8.0 Hz, 1H), 7.99 (d, J＝8.0 Hz,
2H), 7.73—7.69 (m, 3H), 7.60 (d, J＝9.2 Hz, 2H), 7.59
(d, J＝8.4 Hz, 1H), 7.43 (t, J＝7.2 Hz, 1H), 7.02 (d, J＝
9.2 Hz, 2H), 6.87 (s, 1H), 3.87 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ: 178.4, 163.3, 159.9, 156.3, 144.0,
133.7, 132.1, 129.8, 128.2, 127.5, 126.7, 125.7, 125.2,
124.0, 118.0, 114.4, 107.2, 56.3; MS (70 eV) m/z (%):
57 (100), 328 (M＋); IR (neat) ν: 2924, 1641, 1460, 1373,
－
1
1255, 1031, 820, 776 cm . Anal. calcd for C22H16O3: C
80.47, H 4.91; found C 80.41, H 4.98.
To a suspension of the swollen resin 3 (0.5 g) in THF
(15 mL) was added 30% (aq.) H2O2 (0.5 mL) and stirred
for 1 h at 0 ℃, then at room temperature for 20 min.
The mixture was filtered and the resin was washed with
CH2Cl2 (10 mL×2). The filtrate was washed with H2O
(10 mL×2), dried over MgSO4, and evaporated to dry-
ness in vacuum to afford crude products. The crude
products were further purified by column chromatogra-
phy (eluent: petroleum ether/EtOAc, V/V＝1/8) to af-
ford biaryl-chromen-4-ones 4a—4m.
2-(4'-Chloro-biphenyl-4-yl)-chromen-4-one (4e)
White solid, mp. 178—180 ℃; H NMR (CDCl3, 400
1
MHz) δ: 8.26 (dd, J＝7.6, 2.0 Hz, 1H), 8.02 (d, J＝8.8
Hz, 2H), 7.75—7.70 (m, 3H), 7.63—7.57 (m, 3H), 7.49
—7.42 (m, 3H), 6.89 (s, 1H); 13C NMR (CDCl3, 100
MHz) δ: 178.3, 162.9, 156.2, 143.0, 138.1, 134.4, 133.7,
130.8, 129.1, 128.3, 127.4, 126.8, 125.7, 125.2, 124.0,
118.0, 107.5; MS (70 eV) m/z (%): 57 (100), 332 (M＋);
IR (neat) ν: 2927, 1640, 1605, 1467, 1376, 1095, 908,
－
1
737 cm . Anal. calcd for C21H13O2Cl: C 75.79, H 3.94,
2-Biphenyl-4-yl-chromen-4-one (4a) Pale yellow
solid, m.p. 142—144 ℃; H NMR (CDCl3, 400 MHz)
Cl 10.65; found C 75.72, H 4.03, Cl 10.60.
2-(4'-Floro-3'-methyl-biphenyl-4-yl)-chromen-4-
one (4f) White solid, m.p. 143—145 ℃; H NMR
1
1
δ: 8.24 (dd, J＝8.0, 0.8 Hz, 1H), 7.99 (d, J＝8.4 Hz,
2H), 7.76—7.63 (m, 5H), 7.58 (d, J＝8.4 Hz, 1H), 7.48
(t, J＝7.6 Hz, 2H), 7.44—7.39 (m, 2H), 6.87 (s, 1H);
13C NMR (CDCl3, 100 MHz) δ: 178.4, 163.2, 156.3,
144.4, 139.8, 133.8, 130.6, 129.0, 128.2, 127.7, 127.2,
126.8, 125.8, 125.3, 124.1, 118.1, 107.5; MS (70 eV)
m/z (%): 43 (100), 298 (M＋); IR (neat) ν: 3071, 1647,
(CDCl3, 400 MHz) δ: 8.23 (dd, J＝1.25, 7.95 Hz, 1H),
7.97 (d, J＝8.4 Hz, 2H), 7.72—7.66 (m, 3H), 7.58 (d,
J＝8.4 Hz, 1H), 7.45—7.40 (m, 3H), 7.10 (t, J＝8.9 Hz,
1H), 6.85 (s, 1H), 2.36 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ: 178.4, 163.0, 162.7, 160.3, 156.2, 143.5, 135.5,
135.5, 133.7, 130.3, 130.2, 130.2, 127.4, 126.7, 126.0,
126.0, 125.7, 125.5, 125.3, 125.2, 124.0, 118.0, 115.6,
115.4, 107.4, 14.68, 14.65; MS (70 eV) m/z (%): 210
(40.2), 330 (M＋); IR (neat) ν: 2923, 2853, 1640, 1464,
1373, 1122, 807, 772, 753 cm－1; HRMS calcd for
C22H15FO2 [M]＋ 330.1056, found 330.1053.
2-(4'-chloro-3'-trifluoromethyl-biphenyl-4-yl)-
chromen-4-one (4g) White solid, mp. 210—212 ℃;
1H NMR (CDCl3, 400 MHz) δ: 8.24 (dd, J＝1.2, 7.9 Hz,
1H), 8.03 (d, J＝8.4 Hz, 2H), 7.94 (d, J＝1.7 Hz, 1H),
7.75—7.70 (m, 4H), 7.61 (t, J＝8.1 Hz, 2H), 7.44 (t,
J＝7.6 Hz, 1H), 6.88 (s, 1H); 13C NMR (CDCl3, 100
MHz) δ: 178.2, 162.5, 156.2, 141.6, 138.6, 133.8, 132.2,
132.14, 132.08, 131.6, 131.1, 129.2, 128.9, 127.5, 127.0,
126.2, 126.1, 126.07, 126.01, 125.7, 125.3, 124.1, 124.0,
121.3, 118.0, 107.8; MS (70 eV) m/z (%): 120 (67.9),
－
1
1605, 1466, 1376, 768 cm . Anal. calcd for C21H14O2:
C 84.54, H 4.73; found C 84.60, H 4.66.
2-[4'-(Naphthalen-1-yl)]-phenyl-chromen-4-one
(4b) Yellow solid, m.p. 135—137 ℃; 1H NMR
(CDCl3, 400 MHz) δ: 8.28 (d, J＝8.4 Hz, 1H), 8.08 (d,
J＝8.4 Hz, 2H), 7.97—7.88 (m, 3H), 7.75—7.66 (m,
3H), 7.63 (d, J＝8.4 Hz, 1H), 7.60—7.43 (m, 5H), 6.94
(s, 1H); 13C NMR (CDCl3, 100 MHz) δ: 178.5, 163.3,
156.4, 144.4, 138.9, 133.9, 133.8, 131.3, 130.8, 130.7,
128.5, 128.4, 127.7, 127.0, 126.4, 126.3, 126.0, 125.8,
125.6, 125.4, 124.1, 118.1, 107.7; MS (70 ev) m/z (%):
120 (100), 348 (M＋); IR (neat) ν: 2926, 1638, 1466,
1466, 1376, 912, 742, 650 cm－ 1. Anal. calcd for
C25H16O2: C 86.19, H 4.63; found C 86.15, H 4.71.
2-(4'-Methyl-biphenyl-4-yl)-chromen-4-one (4c)
588
www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 585—589

Optimized Palladium(0)-catalyzed Suzuki Cross-coupling Reaction
400 (M＋, 100); IR (neat) ν: 2924, 2853, 1636, 1462,
1375, 1116, 823, 773, 666 cm－ 1; HRMS calcd for
C22H12ClF3O2 [M]＋ 400.0478, found 400.0474.
4', 4'''-Biflavone (4h) White solid, m.p. ＞300
℃; 1H NMR (CDCl3, 400 MHz) δ: 8.28 (dd, J＝7.9, 1.5
Hz, 2H), 8.09 (d, J＝8.4 Hz, 4H), 7.85 (d, J＝8.4 Hz,
4H), 7.79—7.72 (m, 2H), 7.64 (d, J＝8.1 Hz, 2H), 7.47
(t, J＝7.4 Hz, 2H), 6.93 (s, 2H); 13C NMR (CDCl3, 100
MHz) δ: 178.9, 163.5, 156.7, 143.4, 134.5, 131.9, 128.2,
127.5, 126.3, 125.9,124.3, 118.5, 108.1; HRMS calcd
for C30H18O4 [M]＋ 442.1205, found 442.1204.
127.3, 126.3, 126.1, 124.2, 122.7, 116.0, 107.6; IR (neat)
－
1
ν: 3072, 1643, 1625, 1608 cm ; MS (70 eV) m/z (%):
298 (M＋). Anal. calcd for C21H14O2: C 84.54, H 4.73;
found C 84.50, H 4.67.
Conclusions
In summary, we have developed an improved solid-
phase synthetic method for the preparation of biaryl-
chromen-4-ones with good yields. The easy workup
procedure provides the method that is well-suited for
better building the parallel libraries of biflavones with a
biaryl linkage.
2-Biphenyl-3-yl-chromen-4-one (4i) Pale yellow
1
solid, m.p. 120—123 ℃; H NMR (CDCl3, 400 MHz)
δ: 8.24 (dd, J＝7.9, 1.6 Hz, 1H), 8.12 (t, J＝1.7 Hz, 1H),
7.87 (ddd, J＝7.8, 1.9, 1.2 Hz, 1H), 7.73 (ddd, J＝8.4,
1.5, 1.2 Hz, 1H), 7.69—7.36 (m, 9H), 6.88 (s, 1H); 13C
NMR (CDCl3, 100 MHz) δ: 178.2, 163.2, 156.2, 142.1,
140.0, 133.6, 132.2, 130.3, 129.4, 128.8, 127.8, 127.1,
125.6, 125.2, 125.0, 123.8, 118.1, 107.6; MS (70 eV)
m/z (%): 298 (M ); IR (neat) ν: 3070, 1645, 1609 cm ;
Anal. calcd for C21H14O2: C 84.54, H 4.73; found C
84.59, H 4.69.
Acknowledgement
This work was supported by the National Natural
Science Foundation of China (No. 20802063,
21162032), Science Foundations of Education Office in
Yunnan Province (No. 08Y0035) and the Foundation of
the Key Laboratory of Medicinal Chemistry of Natural
Resource (Yunnan University), Ministry of Education,
China.
＋
－
1
4',3'''-Biflavone (4j) White solid, m.p. 265—267
℃; 1H NMR (CDCl3, 400 MHz) δ: 8.28 (dd, J＝7.9, 1.5
Hz, 2H), 8.21 (d, J＝1.4 Hz, 1H), 8.10 (d, J＝8.4 Hz,
2H), 8.00 (d, J＝8.0 Hz, 1H), 7.84 (d, J＝8.4 Hz, 3H),
7.78—7.72 (m, 2H), 7.70—7.62 (m, 3H), 7.47 (t, J＝7.4
Hz, 2H), 6.94 (s, 2H); 13C NMR (CDCl3, 100 MHz) δ:
178.9, 163.5, 163.3, 156.7, 143.7, 141.3, 134.4, 134.3,
133.1, 131.8, 130.7, 130.2, 128.2, 127.5, 126.3, 126.1,
125.8, 125.7, 125.4, 124.4, 118.6, 118.5, 108.5, 108.1;
HRMS calcd for C30H18O4 [M] ＋ 442.1205, found
442.1207.
References
[1] Bringmann, G.; Günther, C.; Ochse, M.; Schupp, O.; Tasler, S. In
Progress in the Chemistry of Organic Natural Products, Vol. 82,
Eds.: Herz, W.; Falk, H.; Kirby, G. W.; Moore, R. E.; Tamm, C.,
Springer, Vienna, 2001, p. 1.
[2] Chakravarthy, B. K.; Rao, Y. V.; Gambhir, S. S.; Gode, K. D.
Planta Med. 1981, 43, 64.
[3] Kim, H. K.; Son, K. H.; Chang, H. W.; Kang, S. S.; Kim, H. P.
Planta Med. 1999, 65, 465.
[4] Lin, Y.-M.; Flavin, M. T.; Schure, R.; Chen, F.-C.; Sidwell, R.;
Barnard, D. I.; Huffman, J. H.; Kern, E. R. Planta Med. 1999, 65,
120.
[5] Zembower, D. E.; Zhang, H. J. Org. Chem. 1998, 63, 9300.
[6] Amellal, M.; Bronner, C.; Braincon, F.; Haag, M.; Anton, R.;
Landry, Y. Planta Med. 1985, 51, 16.
[7] Lee, H. S.; Oh, W. K.; Kim, B. Y.; Ahn, S. C.; Kang, D. O.; Shin, D.
I.; Kim, J.; Mheen, T.-I.; Ahn, J. S. Planta Med. 1996, 62, 293.
[8] Beretz, A.; Joly, M.; Stoclet, J. C.; Anton, R. Planta Med. 1979, 36,
193.
[9] Yamaguchi, L. F.; Kato, M. J.; Mascio, P. D. Recent Prog. Med.
Plants. 2008, 20, 1.
[10] Thapa, A.; Woo, E. R.; Chi, E. Y.; Sharoar, M. G.; Jin, H. G.; Shin, S.
Y.; Park I. S. Biochemistry 2011, 50, 2445.
[11] Zhou, H. F.; Xie, C. H.; Jian, R. J.; Kang, J.; Li, Y.; Zhuang, C. L.;
Yang, F.; Zhang, L. L.; Lai, L.; Wu, T.; Wu, X. L. Agric. Food Chem.
2011, 59, 3060.
[12] Rahman, M.; Riaz, M.; Desai, U. R. Chem. Biodivers. 2007, 4, 2495.
[13] Ali, S. M.; Ilyas, M. J. Org. Chem. 1986, 51, 5415.
[14] Lin, G.-Q.; Zhong, M. Tetrahedron Lett. 1997, 38, 1087.
[15] Chen, J. J.; Chang, H. W.; Kima, H. P.; Parka, H. Bioorg. Med.
Chem. Lett. 2006, 16, 2373.
[16] Deodhar, M.; Black, D. S.; Chan, D. S.-H.; Kumar, N. Heterocycles,
2010, 80, 1267.
[17] Fitzmaurice, R. J.; Etheridge, Z. C.; Jumel, E.; Woolfson, D. N.;
Caddick, S. Chem. Commun. 2006, 4814.
2,6-Diphenyl-chromen-4-one(4k)
Pale yellow
1
solid, m.p. 149—151 ℃ (from MeOH/H2O); H NMR
(CDCl3, 400 MHz) δ: 8.45 (d, J＝2.3 Hz, 1H), 7.90—
8.02 (m, 3H), 7.62—7.74 (m, 3H), 7.34—7.58 (m, 6H),
6.87 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ: 178.5,
163.4, 155.7, 139.3, 138.4, 132.6, 131.8, 131.6, 129.1,
129.0, 127.8, 127.2, 126.3, 124.1, 123.5, 118.6, 107.6;
MS (70 eV) m/z (%): 298 (M＋); IR (neat) ν: 3072, 1635,
－
1
1496 cm . Anal. calcd for C21H14O2: C 84.54, H 4.73;
found C 84.61, H 4.78.
2,8-Diphenyl-chromen-4-one (4l) White solid,
m.p. 125—127 ℃; 1H NMR (CDCl3, 400 MHz) δ: 8.27
(d, J＝7.8 Hz, 1H), 7.81—7.69 (m, 3H), 7.66—7.62 (m,
2H), 7.59—7.39 (m, 7H), 6.88 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 178.5, 163.1, 153.0, 136.1, 134.6,
132.0, 131.6, 131.6, 129.6, 129.1, 128.5, 128.2, 126.2,
125.2, 125.1, 124.5, 107.0; MS (70 eV) m/z (%): 298
＋
－
1
(M ); IR (neat) ν: 3050, 1643 cm . Anal. calcd for
C21H14O2: C 84.54, H 4.73; found C 84.56, H 4.80.
2,7-Diphenyl-chromen-4-one (4m) Pale yellow
1
solid, m.p. 143—145 ℃; H NMR (CDCl3, 400 MHz)
δ: 8.26 (d, J ＝8.3 Hz, 1H), 7.93—7.97 (m, 2 H), 7.78
(d, J＝1.5 Hz, 1H), 7.61—7.74 (m, 4H), 7.58—7.39 (m,
5H), 6.85 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ: 178.2,
163.6, 156.6, 146.8, 139.1, 131.8, 131.5, 129.0, 128.5,
[18] Huang, X.; Tang, E.; Xu, W. M.; Cao, J. J. Comb. Chem. 2005, 7,
802.
(Sun H.)
Chin. J. Chem. 2012, 30, 585—589
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
589