The Journal of Organic Chemistry
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6.57 (d, J = 16.4 Hz, 1H), 5.46 (d, J = 16.4 Hz, 1H), 3.80 (d, J = 11.6 Hz,
1H), 3.61 (d, J = 11.6 Hz, 1H), 3.17 (dd, J = 11.2 Hz, 17.6 Hz, 1H), 2.87
(d, J = 17.6 Hz, 1H), 2.75 (d, J = 6.0 Hz, 1H), 2.07 (dd, J = 6.8 Hz, 6.8
Hz, 1H) 1.91 (s, 1H); 13C NMR (100 MHz, CDCl3) 143.9, 141.6, 137.3,
133.0, 128.3, 127.0, 126.2, 126.1, 125.7, 124.9, 124.5, 124.2, 68.3, 36.7,
33.8, 32.2, 28.6; HRMS m/z calcd for C19H18O [M + Na+] 285.1255,
found 285.1258.
O-tert-Butyldimethylsilyl((1R*,1aS*,6aS*)-1-((E)-styryl)-
1,1a,6,6a-tetrahydrocyclopropa[a]inden-1-yl)methanol (4jB):
Procedure C. According to the general procedure C, 4jB was formed
in 90% yield (0.253 g) as a gummy liquid after flash column chro-
matography using silica gel (hexanes/EtOAc, 9:1) from 0.196 g of 4jA:
(dt, J = 3.3 Hz, 11.4 Hz, 1H), 3.58 (d, J = 4.2 Hz, 1H), 3.55 (s, 1H),
3.35−3.27 (m, 2H), 2.03−1.86 (m, 1H), 1.81−1.73 (m, 2H), 1.50−1.41
(m, 2H), 1.08 (ddd, J = 0.6 Hz, 8.1 Hz, 8.1 Hz, 1H); 13C NMR (100
MHz, CDCl3) 133.4, 117.4, 67.0, 64.4, 58.9, 32.0, 22.3, 18.7, 15.8;
HRMS m/z calcd for C9H14O2 [M + Na+] 177.0891, found 177.0887.
(Z)-3-(N-p-Toluenesulfonamidoethylidene)-(3aR*,7aS*)-tet-
rahydro-2H-furo[2,3-b]pyran (7k): Procedure B. According to the
general procedure B, 7k was formed in 85% yield (0.127 g) as a gummy
liquid after flash column chromatography using silica gel (hexanes/
EtOAc, 8:2) from 0.071 g of 4k: Rf = 0.5 (hexanes/EtOAc, 6:4); IR
(neat) v 3270, 2931, 2864, 1326, 1159, 1092, 815, 664 cm−1; 1H NMR
̅
(300 MHz, CDCl3) 7.75 (D, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H),
5.23−5.16 (m, 1H), 5.80 (d, J = 3.9 Hz, 1H), 4.88 (t, J = 5.7 Hz, 1H),
4.47 (d, J = 13.5 Hz, 1H), 4.35 (d, J = 13.5 Hz, 1H), 3.83−3.78 (m, 1H),
3.53−3.47 (m, 2H), 3.40 (td, J = 1.8 Hz, 11.4 Hz, 1H), 2.56−2.55 (m,
1H), 2.43 (s, 3H), 1.88−1.81 (m, 2H), 1.56−1.36 (m, 1H), 1.27−1.22
(m, 1H); 13C NMR (100 MHz, CDCl3) 143.6, 142.2, 136.8, 129.7,
127.1, 114.8, 101.1, 68.5, 64.5, 42.2, 41.9, 22.3, 21.5, 20.2; HRMS m/z
calcd for C16H21NO4S [M + Na+] 346.1089, found 346.1096.
Rf = 0.5 (hexanes/EtOAc, 9:1); IR (neat) v 2954, 2429, 2856, 1466,
̅
1255, 1099, 836, 775, 693 cm−1; 1H NMR (400 MHz, CDCl3) 7.36 (d,
J = 7.2 Hz, 1H), 7.25−7.14 (m, 6H), 7.10 (d, J = 7.2 Hz, 2H), 6.57 (d, J =
8.4 Hz, 1H), 5.56 (d, J = 8.4 Hz, 1H), 3.93 (d, J = 10.4 Hz, 1H), 3.84 (d,
J = 10.4 Hz, 1H), 3.25 (dd, J = 6.8 Hz, 10.8 Hz, 1H), 2.94 (d, J = 17.6 Hz,
1H), 2.82 (d, J = 6.4 Hz, 1H), 2.22 (dd, J = 6.8 Hz, 6.8 Hz, 1H), 1.00 (s,
9H), 0.18 (s, 6H); 13C NMR (100 MHz, CDCl3) 144.3, 142.5, 137.9,
132.7, 128.3, 126.7, 126.1, 125.9, 125.8, 125.6, 124.4, 124.2, 67.3, 35.6,
32.7, 32.5, 27.8, 25.9, 18.3, −5.24, −5.26; HRMS m/z calcd for
C25H32OSi [M + Na+] 399.2120, found 399.2117.
((1R*,1aS*,6bR*)-1-((E)-Styryl)-1a,6b-dihydro-1H-
cyclopropa[b]benzofuran-1-yl)methanol (4lA): Procedure A.
According to the general procedure A, 4lA was formed in 87% yield
(0.157 g) as a gummy liquid after flash column chromatography using
silica gel (hexanes/EtOAc, 7:3) from 0.200 g of the corresponding ester:
O-tert-Butyldimethylsilyl((1R*,1aS*,6aS*)-1-vinyl-1,1a,6,6a-
tetrahydrocyclopropa[a]inden-1-yl)methanol (4jD): Procedure
D. According to the general procedure C, 4jD was formed in 75% yield
(0.090 g) as a gummy liquid after flash column chromatography using
silica gel (hexanes/EtOAc, 8:2) from 0.150 g of 4jB: Rf = 0.5 (hexanes/
Rf = 0.5 (hexanes/EtOAc, 6:4); IR (neat) v 3367, 2924, 1475, 1463,
̅
1226, 1016, 748 cm−1; 1H NMR (300 MHz, CDCl3) 7.23 (d, J = 9.6 Hz,
2H), 7.11−6.97 (m, 5H), 6.78 (t, J = 7.2 Hz, 1H), 6.69 (d, J = 7.2 Hz,
1H), 6.55 (d, J = 16.5 Hz, 1H), 5.47 (d, J = 16.5 Hz, 1H), 4.72 (d, J = 5.4
Hz, 1H), 3.58 (dd, J = 11.7 Hz, 18.9 Hz, 2H), 2.87 (d, J = 5.4 Hz, 1H),
2.27 (s, 1H); 13C NMR (100 MHz, CDCl3) 161.3, 137.5, 135.1, 128.9,
128.3, 127.9, 127.0, 126.5, 125.4, 122.0, 121.5, 110.0, 70.1, 66.0, 32.7,
26.8; HRMS m/z calcd for C18H16O2 [M + Na+] 287.1048, found
287.1040.
1
EtOAc, 9:1); H NMR (400 MHz, CDCl3) 7.28 (d, J = 6.8 Hz, 1H),
7.15−7.12 (m, 3H), 5.14 (d, J = 6.4 Hz, 2H), 5.05−5.03 (m, 1H), 3.78
(dd, J = 6.4 Hz, 6.4 Hz, 2H), 3.16 (dd, J = 7.2 Hz, 14.4 Hz, 1H), 2.86 (d,
J = 17.6 Hz, 1H), 2.73 (d, J = 6.4 Hz, 1H), 2.11 (dd, J = 6.8 Hz, 6.8 Hz,
1H), 0.95 (s, 9H), 0.12 (s, 6H); 13C NMR (100 MHz, CDCl3) 144.6,
142.8, 133.8, 126.1, 125.7, 124.5, 124.1, 117.5, 66.7, 35.4, 62.8, 62.4,
27.3, 26.0, 18.4, −5.23; HRMS m/z calcd for C19H28OSi [M + Na+]
323.1807, found 323.1808.
O-tert-Butyldimethylsilyl((1R*,1aS*,6bR*)-1-((E)-styryl)-
1a,6b-dihydro-1H-cyclopropa[b]benzofuran-1-yl)methanol
(4lB): Procedure C. According to the general procedure C, 4lB was
formed in 87% yield (0.195 g) as a gummy liquid after flash column
chromatography using silica gel (hexanes/EtOAc, 9:1) from 0.157 g of
((1R*)-1-Vinyl-1,1a,6,6a-tetrahydrocyclopropa[a]inden-1-yl)-
methanol (4j): Procedure E. According to the general procedure C, 4j
was formed in 95% yield (0.052 g) as a gummy liquid after flash column
chromatography using silica gel (hexanes/EtOAc, 8:2) from 0.090 g of
4lA: Rf = 0.5 (hexanes/EtOAc, 9:1); IR (neat) v 2954, 2929, 2857, 2886,
̅
1
1475, 1463, 1226, 1096, 836, 747 cm−1; 1H NMR (300 MHz, CDCl3)
7.26−7.24 (d, J = 7.5 Hz, 2H), 7.13−7.08 (m, 6H), 6.82−6.74 (t, J =
7.5 Hz, 2H), 6.67 (d, J = 7.5 Hz, 1H), 5.56 (d, J = 16.2 Hz, 1H), 3.87 (d,
J = 3.2 Hz, 1H), 3.77 (d, J = 3.2 Hz, 1H), 2.98 (d, J = 5.4 Hz, 1H), 0.83 (s,
9H), 0.00 (s, 6H); 13C NMR (100 MHz, CDCl3) 160.9, 137.4, 134.0,
128.2, 127.4, 127.2, 125.8, 124.7, 122.3, 120.7, 109.3, 69.4, 64.9, 31.2,
25.7, 24.8, 18.2, −5.1; HRMS m/z calcd for C24H30O2Si [M + Na+]
401.1913, found 401.1914.
4jD: Rf = 0.5 (hexanes/EtOAc, 7:3); H NMR (400 MHz, CDCl3)
7.27−7.25 (m, 1H), 7.14−7.09 (m, 3H), 5.28−5.20 (m, 1H), 5.12−5.04
(m, 2H), 3.74 (d, J = 11.2 Hz, 1H), 3.56 (d, J = 11.2 Hz, 1H), 3.17 (dd,
J = 7.2 Hz, 17.6 Hz, 1H), 2.84 (d, J = 17.6 Hz, 1H), 2.70 (d, J = 6.4 Hz,
1H), 2.03 (dd, J = 6.8 Hz, 1H), 1.80 (s, 1H); 13C NMR (100 MHz,
CDCl3) 144.2, 141.8, 133.1, 126.3, 126.1, 124.7, 124.3, 118.2, 67.9, 36.5,
34.1, 32.2, 28.3; HRMS m/z calcd for C13H14O [M + Na+] 209.0942,
found 209.0937.
(Z)-3-(N-p-Toluenesulfonamidoethylidene)-(3aR*,8bS*)-
3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan (7j): Procedure B.
According to the general procedure B, 7j was formed in 91% yield (0.090
g) as a gummy liquid after flash column chromatography using silica gel
(hexanes/EtOAc, 8:2) from 0.052 g of 4j: Rf = 0.4 (hexanes/EtOAc,
tert-Butyldimethylsilyl((1R*,1aS*,6bR*)-1-vinyl-1a,6b-dihy-
dro-1H-cyclopropa[b]benzofuran-1-yl)methanol (4lD): Proce-
dure D. According to the general procedure D, 4lD was formed in 76%
yield (0.118 g) as a gummy liquid after flash column chromatography
using silica gel (hexanes/EtOAc, 9:1) from 0.195 g of 4lB: Rf = 0.5
1
7:3); nature, gummy; yield, 91%; IR (neat) v 3244, 2921, 2832, 1578,
(hexanes/EtOAc, 9:1); H NMR (300 MHz, CDCl3) 7.24−7.18 (m,
̅
1322, 1253, 777 cm−1; 1H NMR (400 MHz, CDCl3) 7.69 (d, J = 8.0 Hz,
2H), 7.39 (d, J = 6.8 Hz, 1H), 7.28−7.21 (m, 4H), 7.15 (d, J = 7.2 Hz,
1H), 5.56 (d, J = 6.8 Hz, 1H), 5.35−5.31 (m, 1H), 4.66 (dd, J = 6.0 Hz,
6.4 Hz, 1H), 4.33 (d, J = 13.6 Hz, 1H), 3.96 (d, J = 13.6 Hz, 1H), 3.49−
3.67 (m, 3H), 3.22 (dd, J = 8.4 Hz, 16.4 Hz, 1H), 2.83 (d, J = 16.4 Hz,
1H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3) 148.9, 143.5, 142.4,
141.1, 136.7, 129.7, 128.8, 127.1, 127.0, 125.3, 124.8, 115.9, 87.4,68.0,
46.4, 42.2, 38.3, 21.5; HRMS m/z calcd for C20H21NO3S [M + Na+]
378.1140, found 378.1142.
1H), 7.03−7.00 (m, 1H), 6.81−6.76 (m, 1H), 6.71−6.68 (m, 1H),
5.12−5.09 (m, 2H), 4.98 (d, J = 4.5 Hz, 1H), 4.95 (d, J = 3.9 Hz, 1H),
3.79 (d, J = 11.2 Hz, 1H), 3.67 (d, J = 11.2 Hz, 1H), 2.09 (d, J = 4.5 Hz,
1H), 0.83 (s, 9H), 0.00 (s, 6H); 13C NMR (100 MHz, CDCl3) 161.1,
132.0, 128.4, 127.3, 127.2, 124.7, 120.6, 118.8, 109.2, 69.4, 64.2, 30.9,
25.8, 24.6, 18.2, −5.45; HRMS m/z calcd for C18H26O2Si [M + Na+]
325.1600, found 325.1594.
((1R*,1aS*,6bR*)-1-Vinyl-1a,6b-dihydro-1H-cyclopropa[b]-
benzofuran-1-yl)methanol (4l): Procedure E. According to the
general procedure E, 4l was formed in 90% yield (0.066 g) as a gummy
liquid after flash column chromatography using silica gel (hexanes/
EtOAc, 8:2) from 0.118 g of 4lD: Rf = 0.5 (hexanes/EtOAc, 9:1); IR
(neat) 3367, 2924, 1475, 1463, 1226, 1016, 748 cm−1; 1H NMR (300
MHz, CDCl3) 7.29 (d, J = 7.2 Hz, 2H), 7.15−7.09 (m, 1H), 6.91−6.86
(m, 1H), 6.83−6.78 (m, 1H), 5.36−5.12 (m, 3H), 4.79 (d, J = 5,4 Hz,
1H), 3.64 (dd, J = 11.4 Hz, 15.6 Hz, 2H), 2.94 (d, J = 5.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3) 160.9, 129.8, 128.2, 127.4, 124.8, 120.9,
((1R*,6R*,7S*)-7-Vinyl-2-oxabicyclo[4.1.0]heptan-7-yl)-
methanol (4k): Procedure A. According to the general procedure A,
7j was formed in 91% yield (0.071 g) as a gummy liquid after flash
column chromatography using silica gel (hexanes/EtOAc, 8:2) from
0.100 g of the corresponding ester: Rf = 0.5 (hexanes/EtOAc, 7:3);
nature, liquid; yield, 85%; IR (neat) v 3405, 2944, 2859, 1632, 1038, 862
̅
cm−1; 1H NMR (300 MHz, CDCl3) 5.90 (dd, J = 14.1 Hz, 18.0 Hz, 1H),
5.42 (dd, J = 1.8 Hz, 10.2 Hz, 1H), 5.36 (dd, J = 1.8 Hz, 3.0 Hz, 1H), 3.68
394
dx.doi.org/10.1021/jo302204k | J. Org. Chem. 2013, 78, 380−399