Job/Unit: O50019
/KAP1
Date: 23-02-15 13:52:31
Pages: 13
R. Hemelaere, F. Carreaux, B. Carboni
FULL PAPER
(90:10) as the eluent afforded 10aa as a white powder (25 mg, 84%),
ane/EtOAc (95:5, 90:10) as the eluent to afford 17b as a colorless
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m.p. 80–82 °C. 1H NMR (300 MHz, CDCl3): δ = 8.25 (d, J = oil (0.20 g, 55%). H NMR (300 MHz, CDCl3): δ = 7.09–6.99 (m,
8.8 Hz, 2 H), 7.64 (d, J = 8.8 Hz, 2 H), 6.98–6.93 (m, 1 H), 6.89–
6.86 (m, 1 H), 6.75 (dd, J = 7.2, 1.0 Hz, 1 H), 6.00 (ddd, J = 17.0,
10.0, 8.9 Hz, 1 H), 5.54 (d, J = 8.9 Hz, 1 H), 5.30 (dd, J = 10.0,
0.7 Hz, 1 H), 5.22 (dd, J = 17.0, 0.7 Hz, 1 H), 4.00 (dd, J = 8.9,
8.9 Hz, 1 H), 3.96 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
147.7, 147.6, 147.1, 144.6, 136.3, 129.6, 126.5, 123.8, 122.2, 118.9,
116.8, 112.1, 89.0, 57.1, 56.1 ppm. HRMS (ESI+): m/z calcd. for
C17H15NO4 [M + Na]+ 320.0898; found 320.0898.
3 H), 6.63 (d, J = 1.8 Hz, 1 H), 6.54 (d, J = 1.8 Hz, 1 H), 6.13
(ddd, J = 17.1, 10.2, 8.5 Hz, 1 H), 5.18 (d, J = 10.2, 0.8 Hz, 1 H),
5.06 (dd, J = 17.1, 0.8 Hz, 1 H), 4.92 (d, J = 5.6 Hz, 1 H), 4.26
(dd, J = 8.5, 5.6 Hz, 1 H), 4.07 (t, J = 6.5 Hz, 2 H), 3.75 (s, 3 H),
2.60 (t, J = 7.6 Hz, 2 H), 2.49 (br. s, 1 H), 1.96–1.89 (m, 2 H), 1.34
(s, 9 H), 1.33 (s, 9 H), 1.24 (s, 9 H), 1.01 (s, 9 H), 0.19 (s, 3 H),
0.16 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 178.6, 175.7,
175.5, 149.8, 141.9, 141.5, 140.7, 140.6, 136.4, 133.6, 131.3, 124.3,
122.4, 121.4, 120.6, 118.3, 110.1, 75.5, 63.6, 54.7, 49.5, 39.1, 39.0,
38.8, 31.9, 30.4, 27.3, 27.2, 26.3, 19.0, –3.5, –3.6 ppm. HRMS
(ESI+): m/z calcd. for C41H62O9Si [M + Na]+ 749.4061; found
749.4063.
2-[4-(Benzyloxy)benzyl]-7-methoxy-3-vinyl-2,3-dihydrobenzofuran
(10ba): Purification by column chromatography with cyclohexane/
EtOAc (95:5) as the eluent afforded 10ba as a white powder (28 mg,
75%), m.p. = 62–64 °C. 1H NMR (300 MHz, CDCl3): δ = 7.47–
7.32 (m, 5 H), 7.23 (d, J = 8.2 Hz, 2 H), 6.94 (d, J = 8.2 Hz, 2 H),
6.87–6.82 (m, 1 H), 6.80–6.77 (m, 1 H), 6.71–6.69 (m, 1 H), 5.73
(ddd, J = 17.0, 10.2, 8.3 Hz, 1 H), 5.10–5.06 (m, 3 H), 5.03 (d, J =
10.2 Hz, 1 H), 4.77–4.70 (m, 1 H), 3.91 (s, 3 H), 3.84 (dd, J = 8.3,
8.3 Hz, 1 H), 3.25–3.03 (m, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 157.6, 147.5, 144.5, 137.5, 137.1, 130.7, 130.6, 129.2,
128.6, 127.9, 127.5, 121.0, 117.1, 117.0, 114.9, 111.7, 89.8, 70.0,
56.1, 52.2, 39.3 ppm. HRMS (ESI+): m/z calcd. for C25H24O3 [M
+ Na]+ 395.1623; found 395.1624. C25H24O3: calcd. C80.62, H 6.50,
O 12.89; found C 80.60, H 6.51, O 12.92.
4-(1-Hydroxy-2-{2-hydroxy-3-methoxy-5-[3-(pivaloyloxy)prop-
yl]phenyl}but-3-enyl)-2-methoxyphenyl Pivalate (18a): The pro-
cedure was the same as described for the synthesis of compounds
9, with use of 17a (0.20 mmol), followed by purification by column
chromatography with cyclohexane/EtOAc (70:30) as the eluent to
afford 18a as a colorless oil (99 mg, 91%). 1H NMR (300 MHz,
CDCl3): δ = 6.90–6.80 (m, 3 H), 6.53 (d, J = 1.6 Hz, 1 H), 6.46 (d,
J = 1.6 Hz, 1 H), 6.31 (ddd, J = 17.0, 10.1, 8.6 Hz, 1 H), 5.83 (br.
s, 1 H), 5.23–5.15 (m, 2 H), 5.05 (d, J = 6.5 Hz, 1 H), 4.03 (t, J =
6.5 Hz, 2 H), 3.91 (dd, J = 8.6, 6.5 Hz, 1 H), 3.86 (s, 3 H), 3.73 (s,
3 H), 2.55 (t, J = 7.6 Hz, 2 H), 1.91–1.82 (m, 2 H), 1.35 (s, 9 H),
1.24 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 178.5, 176.6,
150.6, 146.5, 141.2, 140.9, 139.2, 136.4, 132.5, 126.5, 121.8, 121.4,
118.9, 118.3, 110.8, 109.3, 75.7, 63.4, 56.0, 55.8, 53.4, 39.0, 38.8,
31.8, 30.5, 27.3, 27.2 ppm. HRMS (ESI+): m/z calcd. for C31H42O8
[M + Na]+ 565.2777; found 565.2781.
2-[4-(Benzyloxy)benzyl]-6-methoxy-3-vinyl-2,3-dihydrobenzofuran
(10ac): Purification by column chromatography with cyclohexane/
EtOAc (90:10) as the eluent afforded 10ac as a colorless oil (24 mg,
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64%). H NMR (300 MHz, CDCl3): δ = 7.48–7.33 (m, 5 H), 7.23
(d, J = 8.5 Hz, 2 H), 6.98–6.95 (m, 3 H), 6.46–6.42 (m, 2 H), 5.78
(ddd, J = 17.0, 10.3, 8.3 Hz, 1 H), 5.14–5.08 (m, 4 H), 4.66 (ddd,
J = 8.3, 7.3, 5.2 Hz, 1 H), 3.79 (s, 3 H), 3.73 (dd, J = 8.3, 8.3 Hz,
1 H), 3.10 (dd, J = 14.3, 7.3 Hz, 1 H), 3.01 (dd, J = 14.3, 5.2 Hz,
1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 160.8, 160.5, 157.6,
137.9, 137.2, 130.5, 129.7, 128.6, 127.9, 127.5, 125.0, 121.4, 116.8,
114.9, 106.1, 96.3, 90.1, 70.0, 55.5, 51.7, 39.6 ppm. HRMS (ESI+):
m/z calcd. for C25H24O3 [M + Na]+ 395.1623; found 395.1623.
4-(1-Hydroxy-2-{2-hydroxy-3-methoxy-5-[3-(pivaloyloxy)propyl-
phenyl]but-3-enyl})-1,2-phenylene Bis(2,2-dimethylpropanoate)
(18b): The procedure was the same as described for the synthesis
of compounds 9, with use of 17b (0.20 mmol), followed by purifica-
tion by column chromatography with cyclohexane/EtOAc (70:30)
as the eluent to afford 18b as a colorless oil (85 mg, 70%). 1H
NMR (300 MHz, CDCl3): δ = 7.08–7.04 (m, 2 H), 6.98–6.95 (m, 1
H), 6.55 (d, J = 1.8 Hz, 1 H), 6.48 (d, J = 1.8 Hz, 1 H), 6.30 (ddd,
J = 17.1, 10.2, 9.0 Hz, 1 H), 5.89 (br. s, 1 H), 5.22 (d, J = 10.2,
1.5 Hz, 1 H), 5.16 (d, J = 17.1, 1.5 Hz, 1 H), 5.06 (d, J = 6.5 Hz,
1 H), 4.04 (t, J = 6.5 Hz, 2 H), 3.89 (dd, J = 9.0, 6.5 Hz, 1 H), 3.86
(s, 3 H), 2.67 (br. s, 1 H), 2.60 (t, J = 7.6 Hz, 2 H), 1.92–1.83 (m,
2 H), 1.34 (s, 9 H), 1.33 (s, 9 H), 1.24 (s, 9 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 178.6, 175.8, 175.7, 146.6, 142.0, 141.5,
141.3, 140.9, 135.8, 132.6, 126.3, 124.3, 122.4, 121.4, 118.6, 109.5,
75.1, 63.5, 56.0, 53.3, 39.1, 39.0, 38.8, 31.8, 30.5, 27.3, 27.2 ppm.
HRMS (ESI+): m/z calcd. for C35H48O9 [M + Na]+ 635.3196; found
635.3188.
3-(4-(tert-Butyldimethylsilyloxy)-3-{1-hydroxy-1-[3-methoxy-4-
(pivaloyloxy)phenyl]but-3-en-2-yl}-5-methoxyphenyl)propyl Pivalate
(17a): The procedure was the same as described for the synthesis
of compounds 8, with use of 15 (0.50 mmol) and 4-formyl-2-meth-
oxyphenyl pivalate (0.50 mmol), followed by purification by col-
umn chromatography with cyclohexane/EtOAc (90:10) as the elu-
ent to afford 17a as a white powder (0.15 g, 48%), m.p. = 127–
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129 °C. H NMR (500 MHz, CDCl3): δ = 6.89–6.83 (m, 3 H), 6.61
(d, J = 1.8 Hz, 1 H), 6.53 (d, J = 1.8 Hz, 1 H), 6.17 (ddd, J = 17.2,
10.2, 8.2 Hz, 1 H), 5.19 (d, J = 10.2 Hz, 1 H), 5.08 (d, J = 17.2 Hz,
1 H), 4.92 (d, J = 6.0 Hz, 1 H), 4.28 (dd, J = 8.2, 6.0 Hz, 1 H),
4.07 (t, J = 6.4 Hz, 2 H), 3.76 (s, 3 H), 3.72 (s, 3 H), 2.60 (t, J =
7.6 Hz, 2 H), 1.94–1.88 (m, 2 H), 1.37 (s, 9 H), 1.25 (s, 9 H), 1.02
(s, 9 H), 0.20 (s, 3 H), 0.15 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 178.6, 176.6, 150.6, 149.7, 140.7, 140.6, 139.2, 137.1,
133.6, 131.4, 121.8, 120.7, 119.0, 118.0, 110.9, 109.9, 76.1, 63.5,
55.8, 54.7, 49.5, 39.0, 38.8, 31.9, 30.4, 27.3, 27.2, 26.3, 19.0, –3.5,
–3.7 ppm. HRMS (ESI+): m/z calcd. for C37H56O8Si [M + Na]+
679.3642; found 679.3640. C37H56O8Si: calcd. C67.65, H 8.59, O
19.48; found C 67.66, H 8.57, O 19.47.
3-{7-Methoxy-2-[3-methoxy-4-(pivaloyloxy)phenyl]-3-vinyl-2,3-di-
hydrobenzofuran-5-yl}propyl Pivalate (19a): The procedure was the
same as described for the synthesis of compounds 10, with use of
18a (0.10 mmol), followed by purification by column chromatog-
raphy with cyclohexane/EtOAc (80:20) as the eluent to afford 19a
as a pale yellow powder (41 mg, 79%), m.p. 84–86 °C. 1H NMR
(300 MHz, CDCl3): δ = 7.06 (m, 1 H), 7.02–6.97 (m, 2 H), 6.66
(br. s, 1 H), 6.55 (br. s, 1 H), 5.94 (ddd, J = 17.0, 10.2, 9.2 Hz, 1
H), 5.39 (d, J = 9.2 Hz, 1 H), 5.24 (dd, J = 10.2, 1.4 Hz, 1 H), 5.19
(dd, J = 17.0, 1.4 Hz, 1 H), 4.09 (t, J = 6.5 Hz, 2 H), 4.02 (dd, J
= 9.2, 9.2 Hz, 1 H), 3.92 (s, 3 H), 3.82 (s, 3 H), 2.66 (t, J = 7.6 Hz,
2 H), 2.01–1.91 (m, 2 H), 1.38 (s, 9 H), 1.24 (s, 9 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 178.6, 176.7, 151.3, 145.8, 144.1,
140.0, 138.6, 136.8, 135.0, 130.4, 122.6, 118.4, 118.3, 116.5, 112.4,
4-(2-{2-(tert-Butyldimethylsilyloxy)-3-methoxy-5-[3-(pivaloyloxy)-
propyl]phenyl}-1-hydroxybut-3-enyl)-1,2-phenylene Bis(2,2-dimethyl-
propanoate) (17b): The procedure was the same as described for the
synthesis of compounds 8, with use of 15 (0.50 mmol) and 4-for-
myl-1,2-phenylene bis(2,2-dimethylpropanoate) (0.50 mmol), fol-
lowed by purification by column chromatography with cyclohex-
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