–
1 1
1
8.9° (c 0.33, CHCl ). IR (KBr) 3423, 2926 1735, 1719, 1647, 1429, 1162, 1078 cm . H-NMR
3
(
CDCl ) δ 0.82 and 1.10 (each 3H, s, Me x 2), 1.1–1.2 (1H, m, bornyl H), 1.25–1.9 (6H, m, bornyl H),
3
a
b
2
.73 (1H, d, J = 13.2 Hz, 10’-H ), 3.0–3.05 ( 1H, m, 1- or 4-H), 3.00 (1H, d, J = 12.6 Hz, 10’-H ), 3.14
(
1H, dd, J = 9.9 and 2.2 Hz, 3-H), 3.25 (1H, dd, J = 9.9 and 2.2 Hz, 2-H), 3.3–3.4 (1H, m, 4- or 1-H),
.64 (3H, s, OMe), 4.02 (1H, ddd, J = 8.2, 4.4, and 3.3 Hz, 2'-H), 4.13 (1H, d, J = 2.7 Hz, OH), 6.39 (1H,
ddd, J = 10.7, 6.3, and 1.9 Hz, 5- or 6-H), 6.43 (1H, ddd, J = 9.3, 6.3, and 1.9 Hz, 6- or 5-H ). MS m/z
3
+
+
3
49 (M – OH), 335 (M – CH O). Anal. Calcd for C H O S: C, 65.57; H, 8.11. Found: C, 65.54; H,
3 20 30 4
8
.25.
(
1R,R )-3-endo-(1S,2R,4R)-2-Hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl}methylsulfinyl)bicy-
s
clo[2.2.2]oct-5-ene-2-endo-carboxamide (16b) Colorless plates. mp 268 °C (decomp). [α]D27 –12.8° (c
–
1 1
0
.35, CHCl ). IR (KBr) 3380, 2940, 1661, 1408, 1075, 966 cm . H-NMR (CDCl ) δ 0.81 and 1.09
3 3
(each 3H, s, Me x 2), 1.05–1.1 (1H, m, bornyl H), 1.35–1.85 (6H, m, bornyl H), 2.82 (1H, d, J = 13.2 Hz,
a
b
1
0'-H ), 2.95–3.0 (1H, m, 1- or 4-H), 2.99 (1H, d, J = 13.2 Hz, 10'-H ), 3.03 (1H, brd, J = 10.4 Hz, 3-H),
.21 (1H, dd, J = 9.9 and 2.7 Hz, 2-H), 3.35–3.5 (1H, m, 4- or 1-H), 4.01 (1H, ddd, J = 7.7, 3.8, and 3.8
3
Hz, 2'-H), 4.08 (1H, d, J = 2.7 Hz, OH), 5.38 (1H, br, NH), 5.77 (1H, br, NH), 6.49 (1H, dd, J = 7.1 and
+
7
.1 Hz, 5- or 6-H ), 6.59 (1H, ddd, J = 7.7, 6.3, and 1.1 Hz, 6- or 5-H). MS m/z 351 (M ). Anal. Calcd for
C H NO S: C, 64.92; H, 8.32, N, 3.99. Found: C, 64.97; H, 8.27; N, 3.92.
1
9
29
3
(
1R,R )-Methyl 9,10-Dihydro-12-endo-{(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-
s
yl}methylsulfinyl-9,10-ethanoanthracene-11-endo-carboxylate (17) Yellow plates. mp 236–238 °C.
α]D27 +9.06° (c 0.20, CHCl ). IR (KBr) 3396, 2938 1732, 1458, 1232, 1076, 1053, 1000 cm . H-
–1 1
[
3
NMR (CDCl ) δ 0.74 and 1.04 (each 3H, s, Me x 2), 0.8–1.9 (7H, m, bornyl H), 2.69 (1H, d, J = 12.6
3
a
b
Hz, 10'-H ), 3.01 (1H, d, J = 12.6 Hz, 10'-H ), 3.33 (1H, dd, J = 9.9 and 2.2 Hz, 11- or 12-H), ), 3.38 (1H,
dd, J = 9.9 and 1.6 Hz, 11- or 12-H), 3.61 (3H, s, OMe), 4.01 (1H, ddd, J = 7.1, 4.4 and 2.7 Hz, 2'-H),
4.15 (1H, d, J = 2.7 Hz, OH), 4.70 (1H, d, J = 2.2 Hz, 9- or 10-H), 5.09 (1H, d, J = 2.2 Hz, 4- or 1-H),
7.1–7.25 (4H, m, ArH x 4), 7.3–7.35 (2H, m, ArH x 2), 7.4–7.45 (1H, m, ArH), 7.45–7.5 (1H, m, ArH).
+
MS m/z 463 (M – 1). Anal. Calcd for C H O S: C, 72.38; H, 6.94. Found: C, 72.15; H, 6.87.
2
8 32 4
Methyl 4-Hydroxybenzoate (18) Colorless plates. mp 125–128 °C (lit.,12 mp 127 °C). IR (KBr) 3312,
–
1 1
1
681, 1607, 1589, 1514, 1435, 1279, 850 cm . H-NMR (CDCl ) δ 3.81 (3H, s, OMe), 5.97 (1H, s,
3
+
OH), 6.97 (2H, d, J = 8.8 Hz, ArH x 2), 7.87 (2H, d, J = 8.8 Hz, ArH x 2). MS m/z 152 (M ). HRMS
calcd for C H O : 152.0473. Found: 152.0484.
8
8 2
Methyl E-3-({(1S,2R,4R,R )-2-Hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl}methylsulfinyl)prop-
s
enoate (19) Colorless oil. [α] 29 –98.6° (c 0.37, CHCl ). IR (neat) 3436, 2953, 1728, 1296, 1078, 1037
D
3
–
1 1
cm . H-NMR (CDCl ) δ 0.85 and 1.08 (each 3H, s, Me x 2), 0.8–1.9 (7H, m, bornyl H), 2.58 (1H, d, J
3
a
b
=
13.2 Hz, 10’-H ), 3.27 (1H, d, J = 13.2 Hz, 10’-H ), 3.62 (1H, d, J = 3.3 Hz, OH), 3.83 (3H, s, OMe),
.12 (1H, ddd, J = 8.2, 3.7, and 3.7 Hz, 2’-H), 6.71 (1H, d, J = 14.8 Hz, CH=), 7.63 (1H, d, J = 15.3 Hz,
CH=). 13C-NMR (CDCl ) δ 20.0 (CH ), 20.6 (CH ), 27.3 (CH ), 30.8 (CH ), 38.7 (CH ), 45.2 (CH),
4
3
3
3
2
2
2
48.6 (C), 51.7 (C), 52.6 (OCH ), 55.1 (CH ), 77.1 (CH), 126.0 (CH), 149.8 (CH), 164.3 (CO). MS m/z
3 2
+
+
2
87 (M + 1), 270 (M – O). HRMS calcd for C H O S: 286.1239. Found: 286.1257.
1
4 22 4
Methyl E-3-({(1S,2R,4R,S )-2-Hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl}methylsulfinyl)prop-
s
enoate (20) Colorless oil. [α] 27 +77.5° (c 0.34, CHCl ). IR (neat) 3408, 2953, 1728, 1296, 1076, 1037
D
3