6580
S. Park et al. / Tetrahedron Letters 52 (2011) 6578–6580
In summary, we have developed an efficient method for the syn-
Table 2 (continued)
thesis of 2-arylacrylic esters via Wittig reaction with (methoxy-
methyl)triphenylphosphonium ylide and subsequent singlet
oxygen ene reaction/tosylation/elimination from commercially
available aryl methyl ketones.
Entry
Methyl enol ether 2 (E:Z)
Product 3
Yielda (%)
72
OMe
8
2i (1:1)
3i
Acknowledgment
F3C
O2N
OMe
We thank for the support of research grant of Kwangwoon Uni-
versity in 2011 for this work.
9
2j (1:0.3)
2k (1:1)
3j
74
67
Supplementary data
OMe
OMe
OMe
Supplementary data associated with this article can be found, in
10
3k
NC
Ph
References and notes
11
12
2l (1:0.5)
3l
68
70
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2m (1:0.8)
3m
OMe
13
14
2n (0.7:1)
2o (0.7:1)
3n
3o
57
7
OMe
NDb
S
a
Isolated yield.
ND, no desired product.
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b
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O
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..
MeO
MeO
O
R
1O2
O
CH3
1
+
CH3
R
R
O
2
4
MeO
H
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17. Typical procedure for 2-arylacrylic ester 3: A 100 mL three-necked round-
bottom flask equipped with dispersion bubbler gas inlet, gas outlet, and a
septum was charged with 2 (1.0 mmol) in dry CH2Cl2 (30 mL), and a tip of
methylene blue was added. To the solution at À78 °C was bubbled molecular
oxygen (O2) with 250 W IR lamp at 1 in distance from the reaction flask. The
reaction was monitored continuously by TLC. TLC after 1 h usually showed no
starting material, then IR lamp was removed. The O2 bubbler and outlet were
removed and the reaction was placed under Ar atmosphere. To the reaction
mixture were added tosyl chloride (1.3 mmol) and DIPEA (2.5 mmol) at 0 °C.
The resulting solution was stirred for 2 h at a slow rising from 0 °C to room
temperature, and then concentrated. The residue was subjected to column
chromatography with EtOAc–hexane (1:15) as eluent to give the
corresponding 2-arylacrylic ester 3.
Scheme 2. Generation of aryl methyl ketone 1 via [2+2] cycloaddition.
To expand the scope of this reaction, we applied the protocol to
methyl enol ethers 2n and 2o, which was prepared from 2-
undecanone and 2-acetylthiophene, respectively (entries 13 and
14 in Table 2). In case of 2n including alkyl group instead of aryl
group, the desired 2-nonylacrylic ester 3n was obtained in 57%
yield using the same reaction condition. However, the reaction of
2o including heteroaromatic group did not provide the corre-
sponding acrylic ester 3o at all. We could isolate only 2-acetylthio-
phene in 70% yield.