T. Miura et al. / Tetrahedron 64 (2008) 9305–9308
9307
4
.2.1. 2-(4-Methoxybenzylidene)-1,3-propylene diacetate, 1b
170.7, 170.8; HRMS (ESI-TOF): calcd for C16
299.1254, found: 299.1215.
H
20
O
4
Na (MþNa)þ:
1
Colorless oil; H NMR (400 MHz, CDCl
.11 (s, 3H, COCH ), 3.82 (s, 3H, OCH ), 4.73 (s, 2H, CH
H, CH
OAc), 6.79 (s, 1H, ]CH), 6.89 (d, J¼8.8 Hz, 2H, ArH-3), 7.20
3
):
d
¼2.10 (s, 3H, COCH
3
),
2
2
3
3
2
OAc), 4.80 (s,
2
4.2.9. 2-(2-Naphthylidene)-1,3-propylene diacetate, 1j
13
ꢀ
1
(
5
d, J¼8.8 Hz, 2H, ArH-2); C NMR (100 MHz, CDCl
3
):
d
¼20.9, 21.0,
Colorless powder; mp 33–34 C; H NMR (400 MHz, CDCl
¼2.11 (s, 3H, COCH ), 2.14 (s, 3H, COCH ), 4.81 (s, 2H, CH OAc), 4.88
(s, 2H, CH
OAc), 7.00 (s, 1H, ]CH), 7.37 (dd, J¼1.7, 8.5 Hz, 1H, ArH),
7.49 (m, 2H, ArH), 7.71 (s, 1H, ArH-1), 7.82 (m, 3H, ArH); C NMR
100 MHz, CDCl ):
3
):
5.3, 60.8, 66.8, 113.9, 127.8, 129.3, 130.2, 134.5, 159.3, 170.8, 170.9;
d
3
3
2
þ
HRMS (ESI-TOF): calcd for C15
H
18
O
5
Na (MþNa) : 301.1046, found:
2
13
3
4
2
01.1066.
(
3
d
¼20.9, 21.0, 60.8, 66.4, 126.40, 126.42, 126.6,
.2.2. 2-(4-Trifluoromethylbenzylidene)-1,3-propylene diacetate, 1c
127.7, 128.05, 128.09, 128.14, 131.3, 132.7, 132.8, 133.1, 134.4, 170.7,
1
þ
Colorless oil; H NMR (400 MHz, CDCl
3
):
d
¼2.09 (s, 3H, COCH
3
),
170.8; HRMS (ESI-TOF): calcd for C18
found: 321.1100.
H
18
O
4
Na (MþNa) : 321.1097,
.13 (s, 3H, COCH ), 4.75 (s, 2H, CH OAc), 4.77 (s, 2H, CH
3
2
2
OAc), 6.85
(
s, 1H, ]CH), 7.37 (d, J¼8.1 Hz, 2H, ArH-2), 7.62 (d, J¼8.1 Hz, 2H,
13
ArH-3); C NMR (100 MHz, CDCl
3
):
d
¼20.8, 20.9, 60.4, 65.8, 124.0
4.2.10. 2-(2-Furylidene)-1,3-propylene diacetate, 1k
1
3
2
1
(
q,
J
C–F¼272 Hz), 125.4 (q,
J
C–F¼3.7 Hz), 129.1, 129.8 (q,
J
C–F
¼
Pale yellow oil; H NMR (400 MHz, CDCl
COCH ), 2.10 (s, 3H, COCH ), 4.73 (s, 2H, CH
CH
OAc), 6.40 (d, J¼3.4 Hz, 1H, ArH-3), 6.42 (dd, J¼1.8, 3.4 Hz, 1H,
ArH-4), 6.49 (s, 1H, ]CH), 7.45 (d, J¼1.8 Hz, 1H, ArH-5); C NMR
(100 MHz, CDCl ):
3
):
d
¼2.09 (s, 3H,
3
2.7 Hz), 132.3, 133.2, 139.0, 170.6, 170.7; HRMS (ESI-TOF): calcd
3
3
2
OAc), 5.10 (s, 2H,
þ
for C15
H
15
3
F O
4
Na (MþNa) : 339.0815, found: 339.0838.
2
13
4
.2.3. 2-(4-Chlorobenzylidene)-1,3-propylene diacetate, 1d
3
d
¼20.9, 21.0, 61.4, 66.4, 111.5, 112.4, 120.9, 128.0,
1
Colorless oil; H NMR (400 MHz, CDCl
3
):
d
¼2.09 (s, 3H, COCH
3
),
143.2, 150.8, 170.7, 171.0; HRMS (ESI-TOF): calcd for C12
14
H O
5
Na
þ
2
.12 (s, 3H, COCH ), 4.74 (s, 2H, CH OAc), 4.75 (s, 2H, CH
3
2
2
OAc), 6.78
(MþNa) : 261.0733, found: 261.0727.
(
s, 1H, ]CH), 7.19 (d, J¼8.4 Hz, 2H, ArH-2), 7.33 (d, J¼8.4 Hz, 2H,
13
ArH-3); C NMR (100 MHz, CDCl
1
calcd for C14
3
):
d
¼20.86, 20.94, 60.5, 66.1,
4.2.11. 2-(2-Thienylidene)-1,3-propylene diacetate, 1l
1
28.7, 130.1, 131.8, 132.9, 133.7, 133.8, 170.6, 170.7; HRMS (ESI-TOF):
Colorless oil; H NMR (400 MHz, CDCl
3
):
OAc), 4.95 (s, 2H, CH
s, 1H, ]CH), 7.04 (dd, J¼3.6, 5.0 Hz, 1H, ArH-4), 7.08 (d, J¼3.6 Hz,
d
¼2.10 (s, 3H, COCH
3
),
þ
H15ClO
4
Na (MþNa) : 305.0551, found: 305.0544.
2.11 (s, 3H, COCH
3
), 4.75 (s, 2H, CH
2
2
OAc), 6.88
(
13
4
.2.4. 2-(4-Methylbenzylidene)-1,3-propylene diacetate, 1e
1H, ArH-3), 7.35 (d, J¼5.0 Hz, 1H, ArH-5); C NMR (100 MHz,
1
Colorless oil; H NMR (400 MHz, CDCl
.11 (s, 3H, COCH ), 2.35 (s, 3H, CH ), 4.74 (s, 2H, CH
H, CH
OAc), 6.81 (s, 1H, ]CH), 7.14 (d, J¼8.4 Hz, 2H, ArH), 7.17 (d,
3
):
d
¼2.09 (s, 3H, COCH
3
),
CDCl
3
):
d
¼20.9, 21.0, 61.1, 66.8,126.9,127.2,127.3,128.9,129.3,137.7,
þ
2
2
3
3
2
OAc), 4.79 (s,
170.7, 170.9; HRMS (ESI-TOF): calcd for C12
277.0505, found: 277.0532.
H
14
O
4
SNa (MþNa) :
2
13
J¼8.4 Hz, 2H, ArH); C NMR (100 MHz, CDCl
3
):
d
¼20.9, 21.0, 21.2,
6
0.8, 66.5, 128.7, 129.2, 130.2, 132.4, 134.5, 137.8, 170.7, 170.8; HRMS
4.2.12. 2-(3-Thienylidene)-1,3-propylene diacetate, 1m
þ
1
(
ESI-TOF): calcd for
C
15
H
18
O
4
Na (MþNa) : 285.1097, found:
Colorless oil;
COCH
ꢁ2), 4.74 (s, 2H, CH
CH), 7.08 (dd, J¼1.2, 5.0 Hz, 1H, ArH-4), 7.26 (m, 1H, ArH-2), 7.32
H
NMR (400 MHz, CDCl
3
):
d
¼2.11 (s, 6H,
2
85.1073.
3
2
OAc), 4.85 (s, 2H, CH
2
OAc), 6.76 (s, 1H,
]
13
4
.2.5. 2-(3-Methylbenzylidene)-1,3-propylene diacetate, 1f
(dd, J¼3.0, 5.0 Hz, 1H, ArH-5); C NMR (100 MHz, CDCl
3
):
d
¼20.9,
1
Colorless oil; H NMR (400 MHz, CDCl
.11 (s, 3H, COCH ), 2.35 (s, 3H, CH ), 4.75 (s, 2H, CH
H, CH
OAc), 6.82 (s, 1H, ]CH), 7.05 (m, 2H, ArH), 7.11 (d, J¼7.8 Hz,
H, ArH), 7.25 (t, J¼7.8 Hz, 1H, ArH-5); C NMR (100 MHz, CDCl
3
):
d
¼2.09 (s, 3H, COCH
3
),
21.0, 61.0, 66.7, 124.8, 125.9, 128.3, 128/7, 130.1, 136.3, 170.7, 170.9;
þ
2
2
1
3
3
2
OAc), 4.79 (s,
HRMS (ESI-TOF): calcd for C12
277.0500.
14
H O
4
SNa (MþNa) : 277.0505, found:
2
13
3
):
d
¼20.9, 21.0, 21.4, 60.7, 66.4, 125.8, 128.3, 128.6, 129.5, 130.8, 134.5,
4.3. Typical procedure for hydrolysis using PPL
1
35.3, 138.0, 170.7, 170.8; HRMS (ESI-TOF): calcd for C15
H
18
O
4
Na
þ
(
MþNa) : 285.1097, found: 285.1112.
To a pale yellow suspension of 124 mg (0.500 mmol, 1 equiv) of
2-benzylidene-1,3-propylene diacetate 1a and 124 mg (100 w/w %)
4
.2.6. 2-(2-Methylbenzylidene)-1,3-propylene diacetate, 1g
of PPL in 3 mL of a 1:1 mixture of DMSO–1/15 M phosphate buffer
(pH 7.0) was stirred at rt for 25 h. The reaction mixture was filtered
on Celite, and washed with AcOEt. The filtrate was added to water,
and then extracted three times with AcOEt. The combined AcOEt
1
Colorless oil; H NMR (400 MHz, CDCl
.12 (s, 3H, COCH ), 2.25 (s, 3H, CH ), 4.67 (s, 2H, CH
H, CH OAc), 6.84 (s, 1H, ]CH), 7.09–7.23 (m, 4H, ArH); C NMR
):
¼19.9, 20.9, 21.0, 60.8, 65.9, 125.7, 128.0, 128.9,
3
):
d
¼2.06 (s, 3H, COCH
3
),
2
2
3
3
2
OAc), 4.77 (s,
13
2
(
100 MHz, CDCl
3
d
4
layers were washed with brine, and dried over anhydrous MgSO .
130.0, 131.3, 133.4, 134.5, 136.5, 170.70, 170.74; HRMS (ESI-TOF):
The mixture was filtered, and the filtrate was evaporated. The crude
product was chromatographed on silica gel with a 2:3 mixture of
AcOEt and hexane to afford 101 mg (98% yield) of 3a.
þ
calcd for C15
H
18
O
4
Na (MþNa) : 285.1097, found: 285.1073.
4
.2.7. 2-(2,4,6-Trimethylbenzylidene)-1,3-propylene diacetate, 1h
1
Colorless oil; H NMR (400 MHz, CDCl
.11 (s, 6H, CH ), 2.27 (s, 3H, CH
ꢁ2), 2.12 (s, 3H, COCH
OAc), 4.78 (s, 2H, CH OAc), 6.62 (s, 1H, ]CH), 6.85 (s, 2H, ArH-
); C NMR (100 MHz, CDCl ):
¼20.1, 20.7, 21.0, 61.0, 65.3, 128.1,
3
):
d
¼1.99 (s, 3H, COCH
3
),
4.3.1. (Z)-2-Hydroxymethyl-3-phenyl-2-propenyl acetate, 3a
1
2
CH
3
3
3
3
), 4.40 (s, 2H,
Colorless oil; H NMR (400 MHz, CDCl
3
):
d
¼2.08 (s, 3H, COCH
OAc), 6.81 (s,
1H, ]CH), 7.23–7.36 (m, 5H, ArH); C NMR (100 MHz, CDCl ):
3
),
2
2
2.64 (br s,1H, OH), 4.28 (s, 2H, CH
2
OH), 4.82 (s, 2H, CH
2
1
3
13
3
d
3
131.4, 132.2, 132.3, 135.7, 136.9, 170.8; HRMS (ESI-TOF): calcd for
d
¼20.9, 60.9, 65.3, 127.5, 128.4, 128.8, 131.5, 135.6, 135.8, 171.5;
þ
þ
C
17
H
22
O
4
Na (MþNa) : 313.1410, found: 313.1383.
HRMS (ESI-TOF): calcd for C12
2
H
14
O
3
Na (MþNa) : 229.0835, found:
29.0806.
4
.2.8. 3-Phenyl-2-propylidene-1,3-propylene diacetate, 1i
1
Colorless oil; H NMR (400 MHz, CDCl
.06 (s, 3H, COCH ), 2.48 (m, 2H, CH
CH]), 2.70 (t, J¼7.3 Hz, 2H,
Ph), 4.55 (s, 4H, CH
OAcꢁ2), 5.81 (t, J¼7.5 Hz,1H, ]CH), 7.18 (m,
H, ArH), 7.28 (m, 2H, ArH); C NMR (100 MHz, CDCl
1.0, 29.6, 35.4, 59.7, 66.5, 126.1, 128.4, 128.5, 129.8, 135.2, 141.0,
3
):
d
¼2.03 (s, 3H, COCH
3
),
4.3.2. (Z)-2-Hydroxymethyl-3-(4-methoxy)phenyl-
2-propenyl acetate, 3b
2
CH
3
2
3
2
1
2
2
Colorless oil; H NMR (400 MHz, CDCl
3
):
), 4.26 (s, 2H, CH
OAc), 6.74 (s, 1H, ]CH), 6.88 (d, J¼8.8 Hz, 2H, ArH-3), 7.19
d
¼2.10 (s, 3H, COCH
3
),
13
3
):
d
¼20.9,
2.57 (br s, 1H, OH), 3.80 (s, 3H, OCH
2H, CH
3
2
OH), 4.83 (s,
2