Synthesis of Natural Products on Solid Phases
ture was heated for 12 h at 90 °C. The resin was separated from the
supernatant solution by filtration and washed two times with
MeOH, acetone, H2O, acetone, and CH2Cl2. 13C NMR (100 MHz,
CDCl3): δ = 22.6*, 28.4*, 29.3*, 30.3 (CH2CH2COOR), 35.5 H, CO2CH3), 3.82 (s, 3 H, OCH3), 6.73 (d, J = 7.4 Hz, 1 H, 6ЈЈ-
(CH2CH2COOR), 51.5 (COOCH3), 56.0 (OCH3), 64.4*, 69.8*, H), 6.87–6.82 (m, 4 H, 5ЈЈ-H, 2Ј-H, 2ЈЈ-H), 7.10 (d, J = 8.4 Hz, 2
CDCl3): δ = 2.60–2.66 (m, 2 H, CH2CH2CO2Me), 2.69–2.63 (m, 2
H, CH2CH2CO2Me), 2.92–2.88 (m, 2 H, CH2CH2CO2Me), 2.96–
2.92 (m, 2 H, CH2CH2CO2Me), 3.67 (s, 3 H, CO2CH3), 3.69 (s, 3
3
3
72.8*, 112.4, 116.0, 117.6 (CHCHCOOMe), 119.0, 119.9, 172.9
H, 3Ј-H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 30.2
(COOR) ppm. FTIR: ν = 3454 (vw), 3084 (w), 3031 (w), 2945 (w),
(CHCHCO2Me), 30.8 (CHCHCO2Me), 35.8 (CHCHCO2Me), 35.9
(CHCHCO2Me), 51.6 (COOCH3), 51.7 (CO2CH3), 56.0 (OCH3),
112.9, 117.2 (2 C, C-2Ј), 120.6, 120.8, 129.3 (2 C, C-3Ј), 134.4,
137.2, 143.5, 151.2, 156.4, 173.3 (CO2CH3), 173.4 (CO2CH3) ppm.
EI-MS (70 eV, 100 °C): m/z (%) = 372 (100) [M]+, 299 (40). HRMS
(C21H24O6): calcd. 372.1573; found 372.1577.
˜
2851 (w), 2603 (vw), 2338 (vw), 2311 (vw), 2247 (vw), 1946 (w),
1875 (w), 1805 (w), 1743 (w), 1727 (w), 1691 (w), 1602 (w) cm–1.
Methyl
3-{4Ј-Methoxy-3Ј-[4ЈЈ-(3-methoxy-3-oxopropyl)phenoxy]-
phenyl}acrylate (34): According to general procedure 2, 150 mg of
resin 33 was suspended in 3.00 mL of MeOH, then 2.00 mg of
KCN was added. After purification via preparative TLC (n-hexane/
ethyl acetate, 10:1Ǟ3:1) 12.0 mg of the target compound could be
isolated in 31% yield starting from Merrifield resin. 1H NMR
Acknowledgments
(500 MHz, CDCl3):
δ
=
2.63 (t, 3J
=
7.8 Hz,
2
H,
CH2CH2COOMe), 2.93 (t, 3J = 7.8 Hz, 2 H, CH2CH2COOMe),
3.67 (s, 3 H, COOCH3), 3.77 (s, 3 H, COOCH3), 3.88 (s, 3 H,
This project has been supported by Bayer Crop Science (Monheim,
Germany), the Fonds der Chemischen Industrie, and the University
of Karlsruhe (TH). We thank Dr. Thierry Muller and Melanie Hill
for their dedicated help on this project.
3
OCH3), 6.20 (d, J = 16.0 Hz, 1 H, CHCHCOOCH3), 6.89 (br. d,
3J = 8.5 Hz, 2 H, 3ЈЈ-H), 6.98 (d, J = 8.5 Hz, 1 H, 5Ј-H), 7.10 (d,
3
4J = 2.0 Hz, 1 H, 2Ј-H), 7.14 (br. d, J = 8.5 Hz, 2 H, 2ЈЈ-H), 7.70
3
4
3
3
(d, J = 2.0, J = 8.5 Hz, 1 H, 6Ј-H), 7.56 (d, J = 16.0 Hz, 1 H,
CHCHCOOCH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 30.2
(CH2CH2COOCH3), 35.8 (CH2CH2COOCH3), 51.6 (2 C, CO-
OCH3), 56.1 (OCH3), 112.5, 116.1 (CHCHCOOCH3), 117.8 (2 C,
C-2ЈЈ), 119.0, 125.3, 127.7, 129.5 (2 C, C-3ЈЈ), 135.2, 144.0
(CHCHCOOCH3), 145.9, 153.0, 155.6, 167.5 (CHCHCOOCH3),
173.3 (CH2CH2COOCH3) ppm. EI-MS (GC-MS, 120 °C): m/z (%)
= 370 (100) [M]+, 339 (9) [M – OCH3]+, 310 (21), 297 (85), 281
(14). HRMS (C21H22O6): calcd. 370.1416; found 370.1418.
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5-Polystyrenemethyloxypentyl 3-[4-(4-Formyl-2-methoxyphenoxy)-
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FTIR: ν = 3649 (vw), 3035 (w), 2843 (w), 2338 (vw), 23112 (vw),
˜
2248 (w), 1947 (w), 1877 (w), 1804 (w), 1691 (w), 1641 (w), 1602
(w), 1451 (w) cm–1.
5-Polystyrenemethyloxypentyl-3-{4-[2-methoxy-4-(3-methoxy-3-oxo-
prop-1-enyl)phenoxy]phenyl}acrylate (36): 200 mg of carbonyl resin
35 was suspended in toluene, then 334 mg (1.00 mmol) of (meth-
oxycarbonylmethylene)triphenylphosphorane was added. The mix-
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supernatant solution by filtration. The resulting resin was washed
two times with MeOH, acetone, H2O, acetone, and CH2Cl2. 13C
NMR (100 MHz, CDCl3): δ = 22.7*, 28.5*, 29.4*, 51.7 (CO2CH3),
55.9 (OCH3), 64.5*, 69.7*, 72.8*, 111.6, 117.4, 118.2, 118.9, 121.7,
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˜
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2338 (vw), 2312 (vw), 2248 (w), 1946 (w), 1877 (w), 1805 (w), 1724
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(w), 1679 (w), 1641 (w), 1601 (w) cm–1.
Methyl 3-{4Ј-[2ЈЈ-Methoxy-4ЈЈ-(3-methoxy-3-oxopropyl)phenoxy]-
phenyl}propanoate (37): 28.0 mg of crude compound 12 was dis-
solved in 10 mL of methanol and catalytic amounts of Pd/C (10%)
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Eur. J. Org. Chem. 2009, 4494–4502
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