1200
T. Fujiwara et al. / Steroids 77 (2012) 1198–1204
CD kext (nm)(
D
e
) (cyclohexane) 229.4 (+67.6), 238.6 (0), 246.0
2.2.9. Methyl (3b,22E)-stigmasta-5,22-dien-3-yl 2,20-binaphthalene-
3,30-dicarboxylate, 10b
(ꢀ50.7); IR (film, CHCl3) Peaks (cmꢀ1) 2951 m, 2870 w, 1722 m,
1447 w, 1329 w, 1281 s, 1198 m, 1136 w, 1065 w, 986 w, 895 w,
687 w; 1H NMR (400 MHz, CDCl3) d = 0.65 (s, 1H), 0.68 (s, 2H),
0.81–2.01 (m, 29H), 2.24–2.49 (m, 2H), 3.59 (S, 1.8H), 3.63 (s,
1.2H), 3.68 (s, 1.2H), 3.69 (s, 1.8H), 3.91 (s, 0.4H), 4.02 (s, 0.6H),
4.63–4.73 (m, 1H), 7.53–7.62 (m, 4H), 7.71–7.77 (m, 2H),
7.83–7.89 (m, 2H), 8.04–8.05 (m, 2H), 8.63 (d, J = 7.80 Hz, 1H),
8.65 (s, 0.5H), 8.77 (s, 0.5H); MS FAB (+) m/z: 767 (M++Na, 100);
HRMS calcd for C48H56O7Na (M++Na): 767.3924, found 767.3915.
Colorless gum; HPLC purity: 98.92%; Rf (AcOEt/n-Hexane: 1/3)
0.83. UV (cyclohexane) kmax
(e) nm 242.4 (77 800), 338.4 (3 800);
CD kext (nm)( ) (cyclohexane) 220.2 (+5.2), 243.6 (+6.4); IR (film,
D
e
CHCl3) Peaks (cmꢀ1) 2955 s, 2870 m, 1720 s, 1445 m, 1283 s,
1198 m, 1136 m, 1063 m, 974 w, 895 w, 692 w; 1H NMR
(400 MHz, CDCl3) d = 0.64–2.18 (m, 43H), 3.64 (s, 3H), 4.54–4.59
(m, 1H), 4.97–5.03 (m, 1H), 5.11–5.25 (m, 2H), 7.53–7.62 (m,
4H), 7.75–7.76 (m, 2H), 7.84–7.86 (m, 2H), 7.97–8.01 (m, 2H),
8.60 (s, 1H), 8.62 (s, 1H); MS FAB (+) m/z: 773 (M++Na, 100); HRMS
calcd for C52H62O4Na (M++Na): 773.4546, found 773.4543.
2.2.5. (3a
,5b)-24-methoxy-24-oxocholan-3-yl methyl 2,20-
binaphthalene-3,30-dicarboxylate, 6b
2.2.10. (3b)-cholesta-5,24-dien-3-yl methyl 2,20-binaphthalene-3,30-
dicarboxylate, 11b
Colorless gum; HPLC purity: 99.45%; Rf (AcOEt/n-Hexane: 1/3)
0.69. UV (cyclohexane) kmax
(e) nm 242.6 (103 300), 338.0 (2
900); CD kext (nm)( ) (cyclohexane) 231.6 (+12.2), 240.8 (0),
D
e
Colorless gum; HPLC purity: 99.50%; Rf (AcOEt/n-Hexane: 1/4)
245.8 (ꢀ8.8); IR (film, CHCl3) Peaks (cmꢀ1) 2949 m, 2868 w,
1722 m, 1445 w, 1281 s, 1225 m, 1198 m, 1136 w, 1065 w,
895 w, 669 w; 1H NMR (400 MHz, CDCl3) d = 0.61 (d, J = 5.04 Hz,
3H), 0.77–1.98 (m, 30H), 2.24–2.46 (m, 2H), 3.64 (S, 3H), 3.69 (s,
3H), 4.64–4.73 (m, 1H), 7.52–7.62 (m, 4H), 7.72–7.88 (m, 4H),
7.97–8.02 (m, 2H), 8.62–8.65 (m, 2H); MS FAB (+) m/z: 751
(M++Na, 100); HRMS calcd for C48H56O6Na (M++Na): 751.3975,
found 751.3979.
0.71. UV (cyclohexane) kmax(e) nm 242.4 (132 100), 338.0 (4
000); CD kext (nm)( ) (cyclohexane) 220.4 (+6.6), 240.4 (+6.3);
D
e
IR (film, CHCl3) Peaks (cmꢀ1) 2945 m, 2855 w, 2341 w, 1720 m,
1445 w, 1283 s, 1196 w, 1136 w, 1065 w, 895 w, 781 m, 669 m;
1H NMR (400 MHz, CDCl3) d = 0.65–2.04 (m, 40H), 3.65 (s, 3H),
4.52–4.60 (m, 1H), 5.08 (t, J = 6.87 Hz, 1H), 5.21–5.26 (m, 1H),
7.53–7.62 (m, 4H), 7.75–7.76 (m, 2H), 7.84–7.86 (m, 2H), 7.97–
8.01 (m, 2H), 8.60 (s, 1H), 8.62(s, 1H); MS FAB (+) m/z: 745
(M++Na, 100); HRMS calcd for C50H58O4Na (M++Na): 745.4233,
found 745.4237.
2.2.6. (3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-5-meth-
ylhexan-2-yl]-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-
cyclopenta[a]phenanthren-3-yl methyl 2,20-binaphthalene-3,30-
dicarboxylate, 7b
2.2.11. (3b,5a
)-4,4-dimethylcholesta-8,24-dien-3-yl methyl 2,20-
binaphthalene-3,30-dicarboxylate, 12b
Colorless gum; HPLC purity: 97.93%; Rf (AcOEt/n-Hexane: 1/4)
Colorless gum; HPLC purity: 98.96%; Rf (AcOEt/n-Hexane: 1/3)
0.77. UV (cyclohexane) kmax(e) nm 242.2 (98 600), 338.2 (2 700);
0.86. UV (cyclohexane) kmax
CD kext (nm)(
(e) nm 243.2 (55 800), 338.8 (4 300);
) (cyclohexane) 223.4 (ꢀ15.9), 232.4 (0), 241.2
CD kext (nm)( ) (cyclohexane) 220.4 (+6.9), 242.6 (+6.9); IR (film,
D
e
D
e
CHCl3) Peaks (cmꢀ1) 2951 w, 2871 w, 1720 w, 1283 w, 1227 s,
1207 s, 1136 w, 1065 w, 895 w, 673 s; 1H NMR (400 MHz, CDCl3)
d = 0.64–2.18 (m, 41H), 3.65 (s, 3H), 4.54–4.59 (m, 1H), 5.23 (d,
J = 5.04 Hz, 1H), 7.53–7.62 (m, 4H), 7.75–7.77 (m, 2H), 7.84–7.87
(m, 2H), 7.97–8.02 (m, 2H), 8.60 (s, 1H), 8.62 (s, 1H); MS FAB (+)
m/z: 747 (M++Na, 100); HRMS calcd for C50H60O4Na (M++Na):
747.4389, found 747.4396.
(+10.5); IR (film, CHCl3) Peaks (cmꢀ1) 2930 w, 2341 w, 1720 w,
1281 w, 1224 m, 1202 m, 1065 w, 681 m; 1H NMR (400 MHz,
CDCl3) d = 0.65–2.01 (m, 45H), 3.64 (s, 3H), 4.50–4.58 (m, 1H),
5.06–5.12 (m, 1H), 7.54–7.61 (m, 4H), 7.73–7.85 (m, 4H),
7.96–8.00 (m, 2H), 8.55–8.63 (m, 2H); MS FAB (+) m/z: 787
(M++Na, 100); HRMS calcd for C53H64O4Na (M++Na): 787.4702,
found 787.4700.
2.2.7. Methyl (3b)-stigmast-5-en-3-yl 2,20-binaphthalene-3,30-
dicarboxylate, 8b
2.2.12. Methyl (3b)-olean-12-en-3-yl 2,20-binaphthalene-3,30-
dicarboxylate, 13b
Colorless gum; HPLC purity: 98.95%; Rf (AcOEt/n-Hexane: 1/3)
Colorless gum; HPLC purity: 97.51%; Rf (AcOEt/n-Hexane: 1/4)
0.88. UV (cyclohexane) kmax(e) nm 242.4 (83 300), 325.8 (4 000);
0.77. UV (cyclohexane) kmax
300); CD kext (nm)(
(e) nm 243.2 (116 700), 338.2 (4
) (cyclohexane) 224.0 (ꢀ21.5), 233.6 (0),
CD kext (nm)( ) (cyclohexane) 221.2 (+5.4), 244.2 (+6.4); IR (film,
D
e
CHCl3) Peaks (cmꢀ1) 2936 m, 2855 m, 1720 s, 1445 w, 1283 s,
1207 m, 1136 m, 1063 m, 895 w, 683 m; 1H NMR (400 MHz, CDCl3)
d = 0.64–2.17 (m, 47H), 3.64 (s, 3H), 4.54–4.59 (m, 1H), 5.23 (dd,
J = 5.04 Hz, 1H), 7.53–7.62 (m, 4H), 7.75–7.77 (m, 2H), 7.84–7.86
(m, 2H), 7.97–8.00 (m, 2H), 8.60 (s, 1H), 8.62 (s, 1H); MS FAB (+)
m/z: 775 (M++Na, 100); HRMS calcd for C52H64O4Na (M++Na):
775.4702, found 775.4708.
D
e
247.6 (+15.0); IR (film, CHCl3) Peaks (cmꢀ1) 2927 w, 2854 w,
1720 w, 1601 w, 1281 w, 1200 m, 1064 w, 704 m, 681 m, 664 m;
1H NMR (400 MHz, CDCl3) d = 0.77–2.20 (m, 47H), 3.63 (s, 3H),
4.50–4.61 (m, 1H), 5.13–5.17 (m, 1H), 7.50–7.61 (m, 4H),
7.74–7.85 (m, 4H), 7.96–8.01 (m, 2H), 8.55–8.63 (m, 2H); MS FAB
(+) m/z: 787 (M++Na, 100); HRMS calcd for C53H64O4Na (M++Na):
787.4702, found 787.4698.
2.2.8. Methyl (3b)-spirost-5-en-3-yl 2,20-binaphthalene-3,30-
dicarboxylate, 9b
2.2.13. Methyl (3b,5a
)-stigmastan-3-yl 2,20-binaphthalene-3,30-
Colorless gum; HPLC purity: 98.78%; Rf (AcOEt/n-Hexane: 1/3)
dicarboxylate, 14b
0.69. UV (cyclohexane) kmax
(
e
) nm 242.4 (84 700), 326.4 (5 000);
Colorless gum; HPLC purity: 99.05%; Rf (AcOEt/n-Hexane: 1/4)
0.80. UV (cyclohexane) kmax ) nm 242.0 (107 300), 326.4 (3
600); CD kext (nm)(
CD kext (nm)( ) (cyclohexane) 222.6 (+7.2), 238.6 (+6.3); IR (film,
D
e
(e
CHCl3) Peaks (cmꢀ1) 2909 m, 2853 m, 1720 s, 1454 m, 1283 s,
1136 m, 1063 m, 980 m, 897 m, 685 w; 1H NMR (400 MHz, CDCl3)
d = 0.76–2.19 (m, 36H), 3.36 (t, J = 5.50 Hz, 1H), 3.44–3.48 (m, 1H),
3.64 (s, 3H), 4.38 (q, J = 3.68 Hz, 1H), 4.52–4.60 (m, 1H), 5.23 (m,
1H), 7.53–7.62 (m, 4H), 7.75 (s, 2H), 7.84–7.86 (m, 2H), 7.97–8.00
(m, 2H), 8.60 (s, 1H), 8.62 (s, 1H); MS FAB (+) m/z: 775 (M++Na,
100); HRMS calcd for C50H56O6Na (M++Na): 775.3975, found
775.3978.
D
e
) (cyclohexane) 232.2 (ꢀ4.2), 240.0 (0),
245.6 (+7.4); IR (film, CHCl3) Peaks (cmꢀ1) 2936 m, 2870 m,
1720 s, 1445 m, 1281 s, 1198 m, 1136 m, 1065 w, 895 w, 681 m;
1H NMR (400 MHz, CDCl3) d = 0.55–1.93 (m, 50H), 3.63 (s, 3H),
4.62–4.67 (m, 1H), 7.53–7.61 (m, 4H), 7.75–7.74 (m, 2H), 7.83–
7.85 (m, 2H), 7.97–8.00 (m, 2H), 8.58 (s, 1H), 8.62(s, 1H); MS FAB
(+) m/z: 777 (M++Na, 100); HRMS calcd for C52H66O4Na (M++Na):
777.4859, found 777.4854.