The Journal of Organic Chemistry
Article
128.0, 128.7, 131.0, 131.7, 133.1, 142.4, 142.6, 157.2. IR (neat, cm−1):
3059, 2944, 2839, 1599, 1489, 1244, 1026, 750. Anal. Calcd for
C20H18O: C, 87.56; H, 6.61. Found: C, 87.45; H, 6.68. HRMS-ESI
(m/z) [M + H]+ calcd for C20H19O 275.1436, found 275.1434.
6-Chloro-4-(2-methoxyphenyl)-2,3-dihydro-1H-cyclopenta[b]-
naphthalene (2o). Colorless heavy liquid. Rf = 0.61 in 1:3 EtOAc/
hexanes. 1H NMR (400 MHz, CDCl3): δ 1.99−2.05 (m, 2H), 2.70 (t,
J = 7.6 Hz, 2H), 3.05 (t, J = 7.2 Hz, 2H), 3.63 (s, 3H), 6.99 (d, J = 8.4
Hz, 1H), 7.04 (dd, J = 7.6 Hz, 1.0 Hz, 1H), 7.11−7.15 (m, 1H), 7.26
(dd, J = 8.8 Hz, 2.0 Hz, 1H), 7.34 (td, J = 7.6 Hz, 1.6 Hz, 1H), 7.43 (s,
1H), 7.57 (s, 1H), 7.64 (d, J = 8.8 Hz, 1H). 13C NMR (100 MHz,
CDCl3): δ 25.5, 32.2, 33.0, 55.4, 111.1, 120.6, 121.6, 124.5, 125.3,
127.1, 129.0, 129.1, 130.4, 131.4, 131.5, 132.4, 143.1, 143.7, 157.0. IR
(neat, cm−1): 3059, 2953, 2835, 1599, 1489, 1244, 754. Anal. Calcd for
C20H17ClO: C, 77.79; H, 5.55. Found: C, 77.85; H, 5.51. HRMS-ESI
(m/z) [M + H]+ calcd for C20H18ClO 309.1046, found 309.1045.
4-(3,4-Dimethoxyphenyl)-6-methoxy-1,3-dihydronaphtho[2,3-
4-(Benzo[d][1,3]dioxol-5-yl)-6,7-dimethoxy-1,3-dihydronaphtho-
[2,3-c]furan (2u). Colorless liquid. Rf = 0.48 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3): δ 3.81 (s, 3H), 4.00 (s, 3H), 4.99 (s,
2H), 5.24 (s, 2H), 6.03 (s, 1H), 6.06 (s, 1H), 6.78−6.90 (m, 2H), 6.94
(d, J = 8.0 Hz, 1H), 7.02 (s, 1H), 7.13 (s, 1H), 7.51 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 55.6, 55.8, 73.0, 73.4, 101.1, 104.4, 106.4, 108.5,
109.6, 117.2, 122.6, 127.4, 129.4, 130.8, 132.1, 135.2, 135.9, 146.9,
147.8, 149.2. IR (neat, cm−1): υ 3075, 2924, 2855, 1254, 1152, 1038,
930. Anal. Calcd for C21H18O5: C, 71.99; H, 5.18. Found: C, 71.85; H,
5.23.
4-(Benzo[d][1,3]dioxol-5-yl)-5,6-dimethoxy-1,3-dihydronaphtho-
[2,3-c]furan (2u′). Colorless liquid. Rf = 0.51 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3): δ 3.28 (s, 3H), 3.94 (s, 3H), 4.84 (d, J =
13.2 Hz, 1H), 4.92 (d, J = 13.2 Hz, 1H), 5.24 (d, J = 0.8 Hz, 2H), 6.00
(dd, J = 6.8 Hz, 6.4 Hz, 2H), 6.75 (dd, J = 7.6 Hz, 1,6 Hz, 1H), 6.78
(d, J = 1.2 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 9.2 Hz, 1H),
7.60 (s, 1H), 7.62 (d, J = 9.2 Hz, 1H). 13C NMR (100 MHz, CDCl3):
δ 56.6, 60.5, 73.3, 73.4, 100.8, 107.3, 109.3, 114.4, 119.1, 120.9, 124.5,
127.2, 129.6, 130.6, 135.4, 135.5, 139.6, 144.4, 146.0, 146.7, 149.9.
Anal. Calcd for C21H18O5: C, 71.99; H, 5.18. Found: C, 72.11; H, 5.09.
Benzylic Oxidation of 2s−2u. A solution of H5IO6 (2.0 equiv)
in acetonitrile (5 mL/1 mmol of 2s/2t/2u) was made by vigorous
stirring. To this solution CrO3 (1.2 mol %) was added, and the mixture
was stirred. 1-Arylnaphthalene (2s/2t/2u, 1.0 equiv) was added to the
above solution under stirring. An exothermic reaction occurred
immediately resulting in the formation of a white precipitate. After
1 h of stirring, acetonitrile was removed by evaporation. The residue
was dissolved in H2O and CH2Cl2, and the two phases were separated.
Then the aqueous phase was extracted with CH2Cl2 two times. The
combined organic layers were washed with brine and then dried over
anhydrous Na2SO4. The solvent was evaporated under reduced
pressure. The residue obtained was purified by column chromatog-
raphy over silica gel by eluting with mixtures of EtOAc/hexanes.
9-Benzo[1,3]dioxol-5-yl-8H-furo[3′,4′:6,7]naphtho[2,3-d][1,3]-
dioxol-6-one (21). Obtained from 2s in 73% yield as a colorless solid,
mp 268−271 °C (lit.24 270−271 °C). Rf = 0.43 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3):24 δ 5.18 (d, J = 14.8 Hz, 1H), 5.23 (d,
J = 14.8 Hz, 1H), 6.08−6.10 (m, 4H), 6.79−6.81 (m, 2H), 6.98 (d, J =
8.4 Hz, 1H), 7.10 (s, 1H), 7.31 (s, 1H), 8.27 (s, 1H). 13C NMR (100
MHz, CDCl3): δ 69.4, 101.5, 101.9, 102.0, 105.3, 109.0, 109.7, 121.7,
122.8, 124.7, 129.6, 131.3, 132.7, 133.4, 138.4, 147.7, 148.3, 148.4,
150.5, 171.5.
5-Benzo[1,3]dioxol-5-yl-8H-furo[3′,4′:6,7]naphtho[2,3-d][1,3]-
dioxol-6-one (22). Obtained from 2s in 16% yield as a colorless solid,
mp 273−275 °C (lit.24 273−277 °C). Rf = 0.42 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3):24 δ 5.38 (s, 2H), 6.06−6.09 (m, 4H),
6.78−6.82 (m, 2H), 6.97 (d, J = 8.0 Hz, 1H), 7.12 (s, 1H), 7.20 (s,
1H), 7.69 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 68.0, 101.2, 101.8,
103.67, 103.71, 108.2, 110.6, 119.0, 119.1, 123.5, 128.4, 130.5, 134.7,
139.9, 140.2, 147.5, 147.7, 148.7, 150.0, 169.8.
4-(3,4-Dimethoxyphenyl)-6,7-dimethoxynaphtho[2,3-c]furan-
1(3H)-one (23). Obtained from 2t in 74% yield as a colorless solid,
mp 214−217 °C (lit.24 216−217 °C). Rf = 0.38 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3):24 δ 3.83 (s, 3H), 3.89 (s, 3H), 3.99 (s,
1
c]furan (2p). Colorless liquid. Rf = 0.46 in 1:1 EtOAc/hexanes. H
NMR (400 MHz, CDCl3): δ 3.73 (s, 3H), 3.86 (s, 3H), 3.96 (s, 3H),
5.02 (s, 2H), 5.24 (s, 2H), 6.90−6.92 (m, 2H), 6.99 (d, J = 8.8 Hz,
1H), 7.07 (d, J = 2.4 Hz, 1H), 7.13 (dd, J = 8.8 Hz, 2.4 Hz, 1H), 7.57
(s, 1H), 7.73 (d, J = 8.8 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ
55.0, 55.7, 55.8, 72.9, 73.2, 104.2, 111.2, 112.4, 117.8, 118.3, 121.5,
129.0, 129.3, 130.7, 131.0, 132.9, 135.2, 137.3, 148.2, 148.8, 157.5. IR
(neat, cm−1): υ 2932, 2838, 2226, 1514, 1213, 1175, 1138, 1028. Anal.
Calcd for C21H20O4: C, 74.98; H, 5.99. Found: C, 74.91; H, 6.05.
4-(Benzo[d][1,3]dioxol-5-yl)-6-methoxy-1,3-dihydronaphtho[2,3-
1
c]furan (2q). Colorless liquid. Rf = 0.36 in 1:3 EtOAc/hexanes. H
NMR (400 MHz, CDCl3): δ 3.78 (s, 3H), 5.03 (s, 2H), 5.26 (s, 2H),
6.05 (d, J = 1.2 Hz, 1H), 6.08 (d, J = 1.2 Hz, 1H), 6.81−6.86 (m, 2H),
6.96 (d, J = 8.0 Hz, 1H), 7.06 (s, 1H), 7.15 (dd, J = 8.8 Hz, 2.4 Hz,
1H), 7.60 (s, 1H), 7.76 (d, J = 8.8 Hz, 1H). 13C NMR (100 MHz,
CDCl3): δ 55.1, 72.9, 73.3, 101.1, 104.4, 108.6, 109.7, 117.8, 118.5,
122.7, 129.1, 129.4, 130.9, 131.9, 133.1, 135.2, 137.5, 147.0, 147.8,
157.6. IR (neat, cm−1): υ 3063, 3003, 2903, 1236, 1165, 1115, 1038.
Anal. Calcd for C20H16O4: C, 74.99; H, 5.03. Found: C, 74.85; H, 5.12.
5-(3,4-Dimethoxyphenyl)-6,8-dihydro-furo[3′,4′:6,7]naphtho[2,3-
d][1,3]dioxole (2r). Colorless liquid. Rf = 0.29 in 1:3 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3): δ 3.86 (s, 3H), 3.96 (s, 3H), 4.98 (s,
2H), 5.24 (s, 2H), 6.00 (s, 2H), 6.84 (s, 1H), 6.87 (d, J = 8.0 Hz, 1H),
6.99 (d, J = 8.0 Hz, 1H), 7.01 (s, 1H), 7.13 (s, 1H), 7.49 (s, 1H). 13C
NMR (100 MHz, CDCl3): δ 55.9, 73.0, 73.4, 101.1, 102.2, 103.9,
111.3, 112.4, 117.8, 121.6, 129.0, 130.7, 130.9, 131.8, 135.5, 136.1,
147.3, 147.7, 148.4, 148.9. IR (neat, cm−1): υ 3057, 2907, 2839, 1236,
1173, 1138, 1105, 1040. Anal. Calcd for C21H18O5: C, 71.99; H, 5.18.
Found: C, 71.83; H, 5.25.
5-Benzo[1,3]dioxol-5-yl-6,8-dihydro-furo[3′,4′:6,7]naphtho[2,3-
d][1,3]dioxole (2s). Colorless liquid. Rf = 0.45 in 1:1 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3):13j δ 4.98 (s, 2H), 5.24 (s, 2H), 6.01 (s,
2H), 6.05 (d, J = 1.6 Hz, 2H), 6.75−6.78 (m, 1H), 6.79 (d, J = 1.2 Hz,
1H), 6.93 (d, J = 8.0 Hz, 1H), 7.00 (s, 1H), 7.13 (s, 1H), 7.50 (s, 1H).
13C NMR (100 MHz, CDCl3): δ 73.0, 73.5, 101.16, 102.1, 103.9,
108.6, 109.8, 117.9, 122.7, 129.0, 130.8, 131.5, 132.0, 135.6, 136.1,
147.0, 147.4, 147.7, 147.8.
4-(3,4-Dimethoxyphenyl)-6,7-dimethoxy-1,3-dihydronaphtho-
[2,3-c]furan (2t). Colorless liquid. Rf = 0.35 in 1:3 EtOAc/hexanes.
1H NMR (400 MHz, CDCl3):13j δ 3.78 (s, 3H), 3.87 (s, 3H), 3.97 (s,
3H), 4.00 (s, 3H), 5.02 (s, 2H), 5.26 (s, 2H), 6.85−7.12 (m, 4H), 7.15
(s, 1H), 7.52 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 55.6, 55.8,
55.9, 73.1, 73.5, 104.5, 106.5, 111.3, 112.4, 117.1, 121.5, 127.4, 129.5,
130.9, 131.1, 135.1, 135.9, 148.3, 148.9, 149.2.
4-(3,4-Dimethoxyphenyl)-5,6-dimethoxy-1,3-dihydronaphtho-
[2,3-c]furan (2t′). Light yellow colored liquid. Rf = 0.44 in 1:3
EtOAc/hexanes. 1H NMR (400 MHz, CDCl3):13j δ 3.25 (s, 3H), 3.85
(s, 3H), 3.94 (s, 6H), 4.84 (d, J = 13.2 Hz, 1H), 4.91 (d, J = 13.2 Hz,
1H), 5.25 (s, 2H), 6.78−6.93 (m, 3H), 7.26−7.30 (m, 1H), 7.60−7.70
(m, 2H). 13C NMR (100 MHz, CDCl3): δ 55.8, 56.6, 60.5, 73.3, 110.2,
111.9, 114.4, 119.0, 120.1, 124.5, 127.1, 129.9, 130.7, 134.5, 135.4,
139.6, 144.5, 147.5, 147.9, 149.9.
3H), 4.06 (s, 3H), 5.20 (d, J = 14.4 Hz, 1H), 5.27 (d, J = 14.4 Hz, 1H),
6.90 (s, 1H), 6.96 (d, J = 8.0 Hz, 1H), 7.05 (d, J = 8.0 Hz, 1H), 7.12
(s, 1H), 7.31 (s, 1H), 8.31 (s, 1H). 13C NMR (100 MHz, CDCl3): δ
55.9, 56.0, 56.1, 69.6, 104.1, 107.7, 111.7, 112.2, 121.4, 121.6, 124.1,
128.6, 129.9, 131.7, 132.2, 137.9, 149.0, 149.3, 150.1, 152.0, 171.7.
4-(Benzo[d][1,3]dioxol-5-yl)-6,7-dimethoxynaphtho[2,3-c]furan-
1(3H)-one (24). Obtained in 75% yield as a yellow colored solid, mp
215−218 °C (lit.13f 217−219 °C). Rf = 0.44 in 1:1 EtOAc/hexanes. 1H
NMR (400 MHz, CDCl3):13f δ 3.86 (s, 3H), 4.06 (s, 3H), 5.22 (s,
2H), 6.08 (s, 1H), 6.11 (s, 1H), 6.84−6.86 (m, 2H), 6.99 (d,
J = 7.6 Hz, 1H), 7.10 (s, 1H), 7.30 (s, 1H), 8.31 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 55.9, 56.1, 69.5, 101.4, 104.0, 107.7, 109.0,
109.5, 121.3, 122.7, 124.2, 129.7, 129.9, 131.7, 131.9, 138.0, 147.6,
148.3, 150.1, 152.0, 171.7.
9932
dx.doi.org/10.1021/jo201918d|J. Org. Chem. 2011, 76, 9919−9933