A convenient solid-phase synthesis of coumarins by TMSOTf-catalyzed intramolecular seleno-arylation of tethered alkenes

Article abstract of DOI:10.1055/s-0031-1290618

TMSOTf-catalyzed intramolecular seleno-arylation of tethered alkenes was performed using polystyrene-supported succinimidyl selenide as the selenium source. This catalytic process provides an efficient method for the regioselective synthesis of dihydrocou

Full text of DOI:10.1055/s-0031-1290618

LETTER
907
A Convenient Solid-Phase Synthesis of Coumarins by TMSOTf-Catalyzed
Intramolecular Seleno-Arylation of Tethered Alkenes
Solid-Phase
S
yn
.
thesis of Co
T
umarins ang,*a,b Wen Li,b Zhangyong Gaob
a
Key Laboratory of Medicinal Chemistry of Natural Resource (Yunnan University), Ministry of Education, P. R. of China
School of Chemical Science and Technology, Yunnan University, No 2 Green Lake North Road, Kunming 650091, P. R. of China
Fax +86(871)5033725; E-mail: tange@ynu.edu.cn
b
Received 12 December 2011
Dedicated to the memory of Prof. Xian Huang
a convenient method for the synthesis of 3,4-2H-coumarin
by the Lewis acid catalyzed intramolecular haloarylation
of tethered alkenes using N-halosuccinimide (NXS) as the
halogen source. Hajra’s work inspired us to construct a
Abstract: TMSOTf-catalyzed intramolecular seleno-arylation of
tethered alkenes was performed using polystyrene-supported suc-
cinimidyl selenide as the selenium source. This catalytic process
provides an efficient method for the regioselective synthesis of di-
hydrocoumarins possessing a seleno functionality, followed by syn coumarin skeleton with seleno functionality using a car-
elimination of selenoxides to provide coumarins in good yields and
bon-based intramolecular seleno-arylation of tethered alk-
purities. Suzuki cross-coupling reaction of the resin-bound bro-
enes.
modihydrocoumarin was also performed, and biphenyl coumarin
was obtained by subsequent cleavage of selenium linker.
Solid-phase organic synthesis has emerged as a powerful
tool for acceleration of drug discovery, allowing the prep-
aration of highly diversified compound libraries because
of its simple workup and its characteristics of parallel syn-
thesis.16 A growing number of literatures have reported
the preparation of the combinatorial library of cou-
marins.17 However, coumarins have been prepared by
modification of coumarin skeleton in most of the reported
solid-phase synthesis.18 Watson and Christiansen19 have
reported a solid-phase synthesis of coumarins from ethyl
malonate bound to Wang resin by means of the Knoeve-
nagel condensation with ortho hydroxyaryl aldehydes.
The substituted coumarin-3-carboxylic acids were isolat-
ed in high purity after cleavage with trifluoroacetic acid.
However, the yields of the products were less than 40%.
In recent years, we have been interested in the application
of organoselenium resins in the synthesis of heterocyclic
compounds20 because organoselenium compounds can be
utilized as synthetic intermediates,21 and the selenium–
carbon bond can be easily broken by various methods.22
We have developed polystyrene-supported selenium-me-
diated heteroatom-based cyclization reactions of tethered
alkenes to prepare flavonoids and quinolones.20a,d Herein,
we report an efficient solid-phase synthesis of coumarins
by Lewis acid catalyzed polymer-supported selenium-me-
diated intramolecular cyclization reaction and the subse-
quent oxidative cleavage of selenium resins. The
selenium-mediated carbon-based cyclization reaction also
provides a general tool for the synthesis of annulated are-
ne heterocycles and carbocycles. Advantages of this
method are ease in operations, odorlessness, and ease in
preparation of the substrates.
Key words: selenium, cyclization, TMSOTf, coumarins, solid-
phase synthesis, carbon–carbon bond formation, catalysis
Coumarins are widely distributed throughout the plant
kingdom. As a ‘privileged’ scaffold,1 coumarins exhibit
interesting biological properties2 such as anti-HIV,3 anti-
HCV,4 cytotoxic,5 antimalarial,6 and antibacterial activi-
ties.7 The prominence of coumarins in natural products
and biologically active molecules has attracted consider-
able interest toward their synthesis. Conventionally, cou-
marins have been prepared from phenols by means of
condensation reactions such as Pechmann or Perkin reac-
tions with carbonyl compounds.8 These methods often re-
quire the use of strong acids and high temperatures (150
°C or more). The scope of these transformations is there-
fore relatively limited. Many attempts have been made to
avoid this impediment and improve the conventional
methods by using microwave irradiation,9 ionic liquid,10
and cation-exchange resins.11 Recent research has cen-
tered on the use of transition-metal-catalyzed and Lewis
acid catalyzed carbon–carbon bond formation leading to
the substituted coumarins.12 However, most of the transi-
tion-metal-catalyzed approaches focus on monosubstitut-
ed coumarins and suffer from regioselectivity problems13
while they are also synthesized through catalytic hy-
droarylation with propiolates.14 Fillion et al.12g found that
the Yb(OTf)3-catalyzed reaction of electron-rich phenols
with substituted Meldrum’s acids proceeded by C-alkyla-
tion/O-acylation to produce 3,4-2H-coumarin products.
However, the increased steric hindrance around the elec-
trophilic alkene leads to a shift in chemoselectivity that
gives chromanones and chromones. Hajra et al.15 reported
Firstly, polystyrene-supported allyl selenide (2) was pre-
pared by allylation of the dark-red polystyrene-supported
selenenyl bromide (1,24 Br: 0.99 mmol/g) with NaBH4 and
3-bromoprop-1-ene.20c The pale-yellow resin 227 was ob-
tained almost quantitatively (FTIR: 3019 cm–1).25 Resin 2
reacted smoothly with N-chlorosuccinimide (NCS) to
give polystyrene-supported succinimidyl selenide (PSSS,
SYNLETT 2012, 23, 907–912
x
x.
x
x.
2
0
1
2
Advanced online publication: 15.03.2012
DOI: 10.1055/s-0031-1290618; Art ID: W76411ST
© Georg Thieme Verlag Stuttgart · New York

908
E. Tang et al.
LETTER
FTIR: 1707 cm–1 with the disappearance of 3019 cm–1), jected to the next cyclization reaction only after being
and in this process we found that in addition to excessive washed with dry CH2Cl2 several times in a nitrogen atmo-
NCS, 3-chloroprop-1-ene was the only byproduct and the sphere without removal from the reaction flask. The cy-
color of PSSS will deepen slightly after washing with sol- clization reaction was monitored by FTIR spectroscopy,
vents (Scheme 1). And then, in the presence of sodium hy- which showed a strong band of the carbonyl absorption at
droxide, cinnamoyl chloride reacted with p-cresol at 40 1740 cm–1. Subsequent treatment of ( )-4a with 30%
°C to provide p-tolyl cinnamate (3a) in yield of 82%,23 H2O2 offered 5a in 78% total yield and 95% purity
and the cyclization of p-tolyl cinnamate (3a) with PSSS (Table 1, entry 12). Experimentally, we have observed
was explored in the presence of 10 mol% Sm(OTf)3 in dry that the yield of 5a decreased to 63% when PSSS was
CH2Cl2 and MeCN at –20 °C to reflux temperature.
stored for two weeks before being used in the cyclization
reaction. Therefore, the one-pot method gives a clear ad-
vantage.
1) NaBH4, THF, DMF, 40 °C
SeBr
Se
2) allyl bromide, THF, r.t.
In order to clarify the structure of the ( )-4a, N-phenylse-
lenosuccinimide (NPSS) was prepared from diphenyl di-
selenide in 72% overall yield.26
1
2
O
NCS, CH2Cl2
0 °C to r.t.
Then NPSS was subjected to the cyclization reaction as
the selenium reagent. In the presence of 10 mol% TMSOTf,
NPSS reacted with 3a in dry CH2Cl2 at –78 °C for two
hours, and then the reaction mixture was kept at –20 °C
for eight hours to afford 6-methyl-4-phenyl-3-(phenylse-
lenyl)-3,4-2H-chromen-2-one [( )-6]28,31 in 50% isolated
yield (Scheme 2).
Cl
NSe
+
O
PSSS
Scheme 1
But the selenium resin-bound product was not obtained
because the IR spectrum of the resulting resin did not
show any absorption of the expected carbonyl group. The
difficulty of the above selenium-mediated cyclization
may be explained by the electron deficiency of the double
bond conjugated with the carbonyl group and the weaker
electrophilicity of PSSS than halosuccinimide. Fortunate-
ly, we observed that in the presence of 10 mol% TMSOTf,
treatment of 3a with PSSS in dry CH2Cl2 at –78 °C to –20
°C for ten hours could afford the corresponding polymer-
supported cyclized product ( )-4a. After being washed
with various solvents, ( )-4a was then treated with 30%
H2O2 to afford 6-methyl-4-phenyl-2H-chromen-2-one
(5a) in good yield and high purity (Table 1, entry 12). The
employment of 10 mol% ZnCl2, AlCl3, FeCl3, and TM-
SOTf provided the product in very low yield when the cy-
clization reaction was performed at 20 °C for 12 hours
(Table 1, entries 6–9). The yield of 5a slightly increased
when using 10 mol% of TMSOTf at –20 °C for 12 hours
(Table 1, entry 11). A longer reaction time and the addi-
tion of double and four times the dose of TMSOTf at –20
°C did not improve the yield of 5a. The yield and the pu-
rity of 5a decreased when 5 mol% of TMSOTf was em-
ployed (Table 1, entries 13–16). No product was obtained
when other Lewis acids such as TiCl4, BF3·OEt2, and Ag-
OTf were used (Table 1, entries 3–5). It is noteworthy that
substrate 3a did not undergo any reaction with PSSS in the
absence of a Lewis acid (Table 1, entry 2).
O
O
O
O
NPSS
TMSOTf (10 mol%)
CH2Cl2, –78 to –20 °C
50%
3a
( )-6
Scheme 2
1
From the H NMR spectrum of ( )-6, a large coupling
constant (3JH–H = 10.8 Hz) was observed between H-3 and
H-4, suggesting that the relative stereochemistry of 3-phe-
nylseleno and 4-phenyl was in trans form which was fa-
vorable to the subsequent syn elimination reaction of
selenoxide. Apparently, in solid-phase reactions, the yield
of the crude product was significantly improved because
excessive 3a was used. Furthermore, after the cyclization
reaction, purification of polymer-supported intermediate
( )-4a was very simple. Intermediate ( )-4a was obtained
only by washing with various solvents.
It should be mentioned that we have examined the cy-
clization reaction of 3a under controlled reaction condi-
tions, but in the absence of NPSS. Neither 6-methyl-4-
phenylchroman-2-one (7) nor 6-methyl-4-phenyl-2-(trim-
ethylsiloxy)-4H-chromene (8) was obtained, but only 3a
was recovered (Scheme 3). Additionally, the compound 7
was not found in the filtrate of the reaction mixture in the
synthesis of the resin ( )-4a. So the resin ( )-4 does not
result from the TMSOTf-catalyzed intramolecular
Friedel–Crafts cyclization followed by the selenylation of
the in situ formed TMS enol ether. Further research is
needed to clarify the mechanism of the TMSOTf-cata-
lyzed selenium-mediated cyclization reaction of the sub-
strates 3.
However, PSSS was not suitable for long-term storage be-
cause of its moisture sensitivity. Given that 3-chloroprop-
1-ene was the only byproduct in the preparation of PSSS,
NCS and 3-chloroprop-1-ene were both easily dissolved
in dry CH2Cl2, and dry CH2Cl2 was used as the solvent in
the next step and resin 2 was very stable, a one-pot synthe-
sis of resin ( )-4a was employed. After completion of the
reaction of resin 2 with NCS, PSSS was obtained and sub-
Synlett 2012, 23, 907–912
© Thieme Stuttgart · New York

LETTER
Solid-Phase Synthesis of Coumarins
909
Table 1 Optimization of Solid-Phase Conditions of Cyclization
O
O
O
Se
O
O
O
PSSSf,
Lewis acid
g
H2O2
CH2Cl2
5a
3a
( )-4a
Entry
1
Lewis acid
Sm(OTf)3
none
Amount of catalyst (mol%) Temp (°C)
Time (h)
12
Yield of 5a (%)a Purity of 5a (%)b
10
–
–20 to refluxc
n.r.
n.r.
n.r.
n.r.
n.r.
<5
–
2
20
12
–
3
TiCl4
10
10
10
10
10
10
10
10
10
10
20
40
5
20
12
–
4
BF3·OEt2
AgOTf
20
12
–
5
20
12
–
6
ZnCl2
20
12
–
7
AlCl3
20
12
<5
–
8
FeCl3
20
12
<5
–
9
TMSOTf
TMSOTf
TMSOTf
TMSOTf
TMSOTf
TMSOTf
TMSOTf
TMSOTf
20
12
<5
–
10
11
12
13
14
15
16
0
12
<5
–
–20
12
16
–
–78 to –20d
–78 to –20d
–78 to –20d
–78 to –20d
–78 to –20e
10
76 (78h)
75
>95
>95
>90
>70
>95
10
10
70
10
53
10
12
76
a Yields of the crude products based on the loading of polystyrene-supported selenenyl bromide (1, Br, 0.99 mmol/g); n.r. = no reaction.
b Determined by HPLC analysis.
c The reaction was performed at –20 °C, 0 °C, 20 °C, 40 °C, and reflux temperature, respectively.
d The reaction was performed at –78 °C for 2 h and then kept the reaction mixture in –20 °C for 8 h.
e The reaction was performed at –78 °C for 2 h and then kept the reaction mixture in –20 °C for 10 h.
f PSSS was prepared and then removed to a Buchner funnel, filtered, washed with dry CH2Cl2, and employed in the cyclization reaction with
3a immediately.
g Resin ( )-4a was treated with 30% aq H2O2 at 0 °C for 1 h and then at r.t. for 20 min. The reaction mixture was filtered, and the resin was
washed with CH2Cl2. The filtrate was washed with H2O, dried over MgSO4, and evaporated to dryness in vacuum to afford 5a.
h Compound 5a was synthesized in the one-pot procedure.
Then the polystyrene-supported selenium-mediated cy- and R4 were H and donating-electron substituents such as
clization reactions of a series of substituted cinnamates 3 alkoxyl and alkyl substituents, the carbon-based ring-clo-
in the one-pot procedure were studied. The results are sure reaction proceeded smoothly to give the cyclized
summarized in Table 2. It was obvious when R1, R2, R3, compounds (Table 2, entries 1–21). No cyclized products
O
OTMS
O
O
O
O
TMSOTf (10 mol%)
+
CH2Cl2, –78 to –20 °C
3a
7
8
Scheme 3
© Thieme Stuttgart · New York
Synlett 2012, 23, 907–912

910
E. Tang et al.
LETTER
Table 2 Solid-Phase Synthesis of Coumarins 529
O
O
O
O
O
O
[PSSS]
R4
R1
R4
R1
TMSOTf (10 mol%)
R4
R1
H2O2
R5
R5
R5
CH2Cl2
–78 to –20 °C
R3
R3
R3
R2
R2
R2
3
5
( )-4
Entry
1
R1
H
R2
R3
R4
R5
Ph
Ph
Ph
Yield of 5 (%)a Purity (%)b
Me
H
H
5a 78
5b 82
5c 75
5d 83
5e 76
5f 85
5g 80
5h 82
5i 82
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>95
>90
>90
>90
>90
>90
>90
–
2
OMe
H
H
OMe
H
H
3
H
H
4
H
H
H
H
4-BrC6H4
5
H
H
H
H
4-t-BuC6H4
6
OMe
H
OMe
OMe
H
OMe
H
H
Ph
7
H
Ph
8
H
H
Me
H
Ph
9
Me
Me
Me
Me
H
H
Me
Me
Me
Me
H
Ph
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
H
H
4-MeC6H4
4-MeOC6H4
3-MeOC6H4
4-MeOC6H4
4-MeOC6H4
3-MeOC6H4
3-MeOC6H4
4-MeC6H4
Ph
5j 83
5k 85
5l 80
H
H
H
H
H
H
5m 77
5n 83
5o 76
5p 80
5q 80
5r 78
5s 85
5t 82
5u 83
5ha 58
5hb 52
5hc 55
5ma 63
5mb 59
5mc 52
–
H
Me3
H
H
H
H
H
H
H
Me
Me
H
H
H
H
H
H
H
Me
H
CHMe2
H
H
OEt
OMe
OEt
H
Ph
H
H
H
4-t-BuC6H4
4-t-BuC6H4
H
H
H
H
Me
H
Me
H
H
Me
OMe
H
H
H
H
H
H
H
OMe
H
OMe
H
H
Me
Me
H
H
Me
H
H
H
Me
H
CHO
H
H
H
Ph
H
H
CHO
Ph
–
–
a Yields of the crude products based on the loading of resin 1 (Br, 0.99 mmol/g).
b Determined by HPLC analysis.
Synlett 2012, 23, 907–912
© Thieme Stuttgart · New York

LETTER
Solid-Phase Synthesis of Coumarins
911
were obtained when R1, R2, R3, and R4 were the electron-
withdrawing substituents such as formyl (Table 2, entries
28 and 29). The yield of product 5 apparently decreased
when R5 was H and alkyl (Table 2, entries 22–27).
Furthermore, 4-biphenyl-2H-chromen-2-one (10)30 was
obtained in good yield and purity by Pd(OAc)2-catalyzed
Suzuki cross-coupling reaction of 3-polystyrene-support-
ed seleno-4-(4-bromophenyl)-2H-chromen-2-one [( )-
4d] with phenyl boric acid and subsequent cleavage of the
selenium linker (Scheme 4).
References and Notes
(1) Zhang, L.; Meng, T. H.; Fan, R. H.; Wu, J. J. Org. Chem.
2007, 72, 7279.
(2) Garazd, M. M.; Garazd, Y. L.; Khilya, V. P. Khim. Prir.
Soedin. 2003, 39, 47.
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C.; Bean, M. F.; Taylor, P. B.; Caranfa, M. J.; Breen, A. L.;
Bartus, H. R.; Johnson, R. K.; Hertzberg, R. P.; Westley, J.
W. J. Med. Chem. 1993, 36, 4131.
(4) Wu, J.; Yang, Z.; Fathi, R.; Zhu, Q. US 2004002538, 2004.
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Richomme, P.; Bruneton, J. J. Nat. Prod. 2001, 64, 563.
(6) (a) Köhler, I.; Jenett-Siems, K.; Mockenhaupt, F. P.; Siems,
K.; Jakupovic, J.; González, J. C.; Hernández, M. A.; Ibarra,
R. A.; Berendsohn, W. G.; Bienzle, U.; Eich, E. Planta Med.
2001, 67, 89. (b) Argotte-Ramos, R.; Ramírez-Avila, G.;
Rodríguez-Gutiérrez, M. D. C.; Ovilla-Munõz, M.; Lanz-
Mendoza, H.; Rodríguez, M. H.; González-Cortazar, M.;
Alvarez, L. J. Nat. Prod. 2006, 69, 1442.
In conclusion, we have developed a highly regioselective
selenium-mediated intramolecular Friedel–Crafts alkyla-
tion of substituted phenyl acrylate using polymer-support-
ed organoselenium reagent as a selenium source.
O
O
(7) Verotta, L.; Lovaglio, E.; Vidari, G.; Finzi, P. V.; Neri, M.
G.; Raimondi, A.; Parapini, S.; Taramelli, D.; Riva, A.;
Bombardelli, E. Phytochemistry 2004, 65, 2867.
O
O
PhB(OH)2, KF
Pd(OAc)2 (5 mol%),
o-(biphenyl)PCy2
(8) For selected examples, see: (a) Alexander, V. M.; Bhat, R.
P.; Samant, S. D. Tetrahedron Lett. 2005, 46, 6957.
(b) Hoefnagel, A. J.; Gennewagh, E. A.; Downing, R. S.;
Bekkum, H. V. J. Chem. Soc., Chem. Commun. 1995, 225.
(c) Wu, J.; Diao, T.-N.; Sun, W.; Li, Y. Synth. Commun.
2006, 36, 2949. (d) Sharma, G. V. M.; Reddy, J. J.;
Lakshmi, P. S.; Krishna, P. R. Tetrahedron Lett. 2005, 46,
6119.
Br
THF, r.t.
( )-4d
( )-9
O
H2O2
O
(9) Manhas, M. S.; Ganguly, S. N.; Mukherjee, S.; Jain, A. K.;
Bose, A. K. Tetrahedron Lett. 2006, 47, 2423.
(10) Kumar, V.; Tomar, S.; Patel, R.; Yousaf, A.; Parmar, V. S.;
Malhotra, S. V. Synth. Commun. 2008, 38, 2646.
total yield: 70%
puirity: >90%
10
(11) Gunnewegh, E. A.; Hoefnagel, A. J.; van Bekkum, H.
J. Mol. Catal. A: Chem. 1995, 100, 87.
Scheme 4
(12) For selected examples, see: (a) Yamamoto, Y.; Kirai, N.
Org. Lett. 2008, 10, 5513. (b) Fernandes, T.; Vaz, B. G.;
Eberlin, M. N.; Silva, A. J. M.; Costa, P. R. R. J. Org. Chem.
2010, 75, 7085. (c) Shi, Z.; He, C. J. Org. Chem. 2004, 69,
3669. (d) Jia, C. G.; Piao, D. G.; Oyamada, J. Z.; Lu, W. J.;
Kitamura, T.; Fujiwara, Y. Science 2000, 287, 1992.
(e) Fürstner, A.; Mamane, V. J. Org. Chem. 2002, 67, 6264.
(f) Pastine, S. J.; Youn, S. W.; Sames, D. Org. Lett. 2003, 5,
1055. (g) Youn, S. W.; Pastine, S. J.; Sames, D. Org. Lett.
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A.; Malhotra, N. R.; Sitler, T. C. J. Org. Chem. 2006, 71,
409.
(13) For selected examples, see: (a) Rayabarapu, D. K.;
Sambaiah, T.; Cheng, C.-H. Angew. Chem. Int. Ed. 2001, 40,
1286. (b) Yoneda, E.; Sugioka, T.; Hirao, K.; Zhang, S.-W.;
Takahashi, S. J. Chem. Soc., Perkin Trans. 1 1998, 477.
(c) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1996, 118,
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Chung, Y. K. Synlett 2004, 2541.
Among the catalysts investigated, TMSOTf was found to
be the best one. The one-pot methodology for the synthe-
sis of polymer-supported cyclized intermediate could
avoid the decrease of total yield of the product, which was
caused by the moisture sensitivity of PSSS. The target
products were obtained in good yields and purities by the
cleavage of the selenium linker. Furthermore, the easy
workup procedure and easily prepared substrates provide
an approach that is well-suited for building the parallel li-
braries upon the basis of further transformation of poly-
mer-supported 3,4-2H-chromen-2-ones [( )-4]. The
further modifications of resin [( )-4] are still under way.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.
Acknowledgment
(14) For selected examples, see: (a) Jia, C.; Piao, D.; Kitamura,
T.; Fujiwara, Y. J. Org. Chem. 2000, 65, 7516.
Thanks to the National Natural Science Foundation of China (Pro-
ject No. 20802063, 21162032) and the Foundation of Key Labora-
tory of Medicinal Chemistry of Natural Resource, Ministry of
Education, China.
(b) Kitamura, T.; Yamamoto, K.; Kotani, M.; Oyamada, J.;
Jia, C.; Fujiwara, Y. Bull. Chem. Soc. Jpn. 2003, 76, 1889.
(c) Kotani, M.; Yamamoto, K.; Oyamada, J.; Fujiwara, Y.;
Kitamura, T. Synthesis 2004, 1455. (d) Oyamada, J.;
Kitamura, T. Tetrahedron 2006, 62, 6918. (e) Shi, Z.; He,
C. J. Org. Chem. 2004, 69, 3669. (f) Li, K.; Zeng, Y.;
Neuenswander, B.; Tunge, J. A. J. Org. Chem. 2005, 70,
© Thieme Stuttgart · New York
Synlett 2012, 23, 907–912

912
E. Tang et al.
6515.
LETTER
After filtering and concentrating under reduced pressure by
rotary evaporation at r.t, the oily residue was subjected to
preparative TLC on silica gel with EtOAc–light PE (1:9) as
eluent to give 197 mg of ( )-6 (50% isolated yield).
(29) General Procedure for the Preparation of 2H-Chromen-
2-one (5)
(15) Hajra, S.; Maji, B.; Karmakar, A. Tetrahedron Lett. 2005,
46, 8599.
(16) (a) In Organic Synthesis on Solid-Phase; Dörwald, F. Z.,
Ed.; Wiley-VCH: Weinheim, 2000. (b) In Handbook of
Combinatorial Chemistry; Nicolaou, K. C.; Hanko, R.;
Hartwig, W., Eds.; Wiley-VCH: Weinheim, 2002.
(c) Eynde, J. J. V.; Rutot, D. Tetrahedron 1999, 55, 2687.
(d) Watson, B. T.; Christiansen, G. E. Tetrahedron Lett.
1998, 39, 6087.
(17) (a) Wu, J.; Liao, Y.; Yang, Z. J. Org. Chem. 2001, 66, 3642.
(b) Bussolari, J. C.; Rehborn, D. C.; Combs, D. W.
Tetrahedron Lett. 1999, 40, 1241.
(18) (a) Song, A.; Zhang, J.-H.; Lam, K. S. J. Comb. Chem. 2004,
6, 112. (b) Song, A.; Zhang, J.-H.; Lebrilla, C. B.; Lam, K.
S. J. Comb. Chem. 2004, 6, 604.
(19) Watson, B. T.; Christiansen, G. E. Tetrahedron Lett. 1998,
39, 6087.
(20) (a) Huang, X.; Tang, E.; Xu, W. M. J. Comb. Chem. 2005, 7,
802. (b) Tang, E.; Huang, X.; Xu, W. M. Tetrahedron 2004,
60, 9963. (c) Xu, W. M.; Huang, X.; Tang, E. J. Comb.
Chem. 2005, 7, 726. (d) Tang, E.; Chen, B. Z.; Zhang, L. P.;
Li, W.; Lin, J. Synlett 2011, 707.
(21) Petragnani, N.; Stefani, H. A.; Valduga, C. J. Tetrahedron
2001, 57, 1411.
(22) Nicolaou, K. C.; Pfefferkorn, J. A.; Cao, G. Q.; Kim, S.;
Kessabi, J. Org. Lett. 1999, 1, 807.
(23) Majumder, P. L.; Chatterjee, S.; Mukhoti, N. J. Indian
To a suspension of the swollen resin 2 (1.0 g) in dry CH2Cl2
(15 mL) was added NCS (0.668 g, 5.0 mmol) at 0 °C. The
mixture was stirred for 0.5 h at 0 °C and 2 h at r.t. After
filtrating and washing with dry CH2Cl2 (3 × 15 mL), PSSS
was suspended with dry CH2Cl2 (15 mL) and cooled to –78
°C. TMSOTf (0.022 g, 0.10 mmol) was added. After stirring
for 0.5 h at –78 °C, substituted phenyl acrylate 3 (5.0 mmol)
was added under nitrogen atmosphere. The suspension was
stirred for another 2 h at –78 °C and then stored in a freezer
at –20 °C for 8 h. Saturated aq NaHCO3 (5 mL) was poured
into the flask to quench the reaction mixture. 3-Polystyrene-
supported seleno-3,4-2H-chromen-2-one [( )-4] was
collected by filtration, washed with THF (2 × 20 mL), Et2O
(2 × 20 mL), THF–H2O (3:1, 2 × 20 mL), H2O (2 × 20 mL),
THF (2 × 20 mL), benzene (2 × 20 mL), MeOH (2 × 20 mL),
and CH2Cl2 (2 × 20 mL), and dried under vacuum. The
washed resin ( )-4 was suspended in THF (15 mL). To the
mixture was added 30% aq H2O2 (1.2 mL). The mixture was
stirred for 1 h at 0 °C and then for another 20 min at r.t. The
mixture was filtered, and the resin was washed with CH2Cl2
(2 × 15 mL). The filtrate was washed with H2O (2 × 30 mL),
dried over MgSO4, and evaporated to dryness in vacuum to
afford 2H-chromen-2-ones 5.
Chem. Soc. 2001, 78, 743.
(24) Nicolaou, K. C.; Pastor, J.; Barluenga, S.; Winssinger, N.
Chem. Commun. 1998, 1947.
(25) Xu, W. M.; Tang, E.; Huang, X. Tetrahedron 2005, 61, 501.
(26) Hori, T.; Sharpless, K. B. J. Org. Chem. 1979, 44, 4208.
(27) Typical Procedure for the Preparation of Polystyrene-
Supported Allyl Selenide (2)
(30) Typical Procedure for the Preparation of 4-Biphenyl-
2H-chromen-2-one (10)
To a suspension of the swollen resin ( )-4d (0.5 g) in dry
THF (15 mL) was added Pd(OAc)2 (0.0056 g, 0.025 mmol),
phenylboronic acid (0.61 g, 5.0 mmol), KF (0.58 g, 10.0
mmol), and 2-(dicyclohexylphosphino)biphenyl [o-
(biphenyl)PCy2] (0.175 g, 0.5 mmol) under a nitrogen
atmosphere. The reaction mixture was stirred at r.t. for 24 h.
Resin ( )-9 was collected by filtration, washed with THF (2
× 20 mL), Et2O (2 × 20 mL), THF–H2O (3:1, 2 × 20 mL),
H2O (2 × 20 mL), THF (2 × 20 mL), benzene (2 × 20 mL),
MeOH (2 × 20 mL), and CH2Cl2 (2 × 20 mL), and dried in
vacuum. The washed resin ( )-9 was suspended in THF (15
mL). To the mixture was added 30% aq H2O2 (1.5 mL) and
stirred for 1.5 h at 0 °C, and stirred for another 20 min at r.t.
The mixture was filtered, and the resin was washed with
CH2Cl2 (2 × 15 mL). The filtrate was washed with H2O (2 ×
30 mL), dried over MgSO4, and evaporated to dryness under
vacuum to afford 4-biphenyl-2H-chromen-2-one (10).
(31) 6-Methyl-4-phenyl-3-(phenylselenyl)-2H-chromen-2-one
[( )-6]
To a suspension of the swollen polystyrene-supported
selenenyl bromide (1, Br: 0.99 mmol/g, 2.5 g) in dry THF–
DMF (v/v = 5:1, 30 mL) was added NaBH4 (5 mmol) under
nitrogen atmosphere at 40 °C. After stirring for 8 h at 40 °C,
3-bromoprop-1-ene (5.5 mmol) was added dropwise under
nitrogen atmosphere, and stirred for another 12 h. The resin
2 was collected by filtration, washed with THF (2 × 20 mL),
MeOH (2 × 20 mL), and CH2Cl2 (2 × 20 mL), and dried in
vacuum.
(28) Typical Procedure for the Preparation of 6-Methyl-4-
phenyl-3-(phenylselenyl)-2H-chromen-2-one [( )-6]
To an oven-dried flask (25 mL) was added polystyrene-
supported succinimidyl selenide (PSSS, 0.27 g, 1.05 mmol)
in dry CH2Cl2 (10 mL) under nitrogen atmosphere, and the
solution was cooled at –78 °C. Trimethylsilyl trifluoro-
methanesulfonate (TMSOTf, 0.022 g, 0.1 mmol) was added.
After stirring for 0.5 h at –78 °C, p-tolyl cinnamate (0.238 g,
1.0 mmol) was added under nitrogen atmosphere. The
mixture was stirred for another 2 h at –78 °C and then stored
in a freezer at –20 °C for 8 h. Saturated aq NaHCO3 (5 mL)
was poured into the flask to quench reaction mixture. The
organic phase was separated, and the aqueous phase was
extracted with fresh portion of CH2Cl2 (25 mL). The extracts
were combined, washed with H2O, and dried over MgSO4.
Yellow oil. 1H NMR (400 MHz, CDCl3): d = 7.35–7.07 (11
H, m), 6.86 (2 H, dt, J1 = 8.4 Hz, J2 = 2.8 Hz), 4.58 (1 H, d,
J = 10.8 Hz), 4.04 (1 H, d, J = 10.4 Hz), 2.33 (3 H, s). 13
NMR (100 MHz, CDCl3): d = 170.10, 148.59, 135.90,
135.65, 135.47, 129.97, 129.07, 128.96, 128.78, 128.54,
128.44, 127.79, 121.12, 79.10, 51.07, 20.96. IR (KBr):
C
n = 1741, 1496, 1431, 1208, 1010, 736, 693 cm–1. HRMS:
m/z [M]+ calcd for C22H18O2Se: 394.0472; found: 394.0470.
Synlett 2012, 23, 907–912
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