H. Muratake et al. / Tetrahedron 60 (2004) 11783–11803
11799
dissolved in MeOH (3 ml) and to this was added NaBH4
(8 mg, 0.211 mmol). The mixture was stirred at 22 8C for
30 min. Saturated NH4Cl–H2O was added and the whole was
extracted with CH2Cl2. Usual work-up and PTLC [benzene–
EtOAc (5:1)] provided (40aR*,90aS*K30,400,90, 90a-tetrahy-
drospiro[1,3-dioxolane-2,10[1H]fluorene]-4 a-(20H)-metha-
nol (75, 6.5 mg, 17% overall) and (4aR*, 9aS*0,10S*)-
3,4,4a,9,9a,10-hexahydrospiro[anthracene-1(2H),2 -[1,3]-
dioxolan]-10-ol (76, 11.5 mg, 29% overall) in order of
decreasing polarity.
manner as for the procedure of Table 2, run 2, 20-cis (30 mg,
85.0 mmol) was stirred under reflux in toluene (4 ml) with
PdCl2(Ph3P)2 (6 mg, 8.55 mmol) and Cs2CO3 (83 mg,
0.255 mmol) under an Ar atmosphere for 3 h. Saturated
NH4Cl–H2O was added and the mixture was extracted with
CH2Cl2. Usual work-up and PTLC [hexane–CH2Cl2 (1:1)]
gave (40aS*,100aS*)-30,40,100,1000a-tetrahydrospiro[1,3-
dioxolane-2,10(20H)-phenat0hrene]-4 a(90H)-carboxaldehyde
(68-trans, 5 mg, 22%), (4 aR*,100aS*)-30,40,100,1000a-tetra-
hydrospiro[1,3-dioxolane-2,10(20H)-phenathrene]-4 a(90H)
carboxaldehyde (68-cis, 12 mg, 52%), and a mixture of
69-trans and -cis (2 mg) in order of increasing polarity. The
mixture was further purified by PTLC [benzene–EtOAc
(59:1)] to yield (4aR*,11aS*)-3,4,4a,10, 11,11a-hexahydro-
spiro[1H-dibenzo[a,d]cycloheptene-1,20-[1,3]-dioxolan]-
5(2H)-one (69-trans, less than 0.5 mg, trace) and (4aS*,
11aS*)-3,4,4a,10,11,11a-hexahydrospiro-[1H-dibenzo[a,d]-
cycloheptene-1,20-[1,3]-dioxolan]-5(2H)-one (69-cis,
1.5 mg, 6%) in order of increasing polarity.
Compound 75. Colorless syrup. DI–HRMS calcd for
C16H20O3: 260.1411. Found: 260.1415. DI–MS m/z: 260
(MC, 10), 229 (38), 128 (23), 115 (17), 99 (100), 86 (20), 55
1
(23). H NMR (300 MHz) d: 1.33 (1H, ddd, JZ14, 12.5,
4 Hz), 1.54–1.64 (1H, m), 1.64–1.96 (4H, m), 2.59 (1H, dd,
JZ11, 9 Hz), ca. 2.63 (1H, br s, OH), 2.92 (1H, dd, JZ16,
11 Hz), 3.04 (1H, dd, JZ16, 9 Hz), 3.86 (1H, br d, JZ
11 Hz), 3.91–4.11 (4H, m), 4.10 (1H, br d, JZ11 Hz), 7.08–
7.28 (4H, m). 13C NMR d: 20.7, 30.3, 32.4, 33.7, 49.5, 52.4,
64.3 (2C), 68.8, 110.5, 121.4, 124.8, 126.4, 126.8, 141.2,
148.8.
Compound 68-trans. Colorless prisms, mp 114–116 8C
(hexane). GC–HRMS calcd for C17H20O3: 272.1411.
Found: 272.1429. GC–MS m/z: 272 (MC, 0.6), 244 (11),
182 (30), 129 (17), 128 (18), 115 (11), 99 (100), 55 (32). IR
(CHCl3) cmK1: 1712. 1H NMR (300 MHz) d: 1.42–1.58
(1H, m), 1.27 (1H, dddd, JZ13, 13, 4, 2 Hz), 1.69–1.95 (3H,
m), 2.05–2.24 (3H, m), 2.91–3.06 (3H, m), 3.90–4.08 (4H, m),
7.10–7.19 (3H, m), 7.20–7.25 (1H, m), 9.85 (1H, d, JZ2 Hz).
Compound 76. Colorless syrup. GC–HRMS calcd for
C16H20O3: 260.1411. Found: 260.1415. GC–MS m/z: 260
(MC, 22), 242 (11), 217 (17), 198 (15), 159 (100), 141 (22),
1
99 (51), 91 (22), 86 (27), 55 (19). H NMR (90 MHz) d:
0.87–2.10 (8H, m, including OH), 2.34 (1H, br d, JZ12 Hz),
2.78 (2H, d, JZ7 Hz), 4.00 (4H, s), 4.20–4.54 (1H, m,
changed to 4.36, d, JZ9 Hz with D2O), 6.94–7.40 (3H, m),
7.40–7.71 (1H, m).
Compound 68-cis. Colorless prisms, mp 131–133 8C
(CH2Cl2–hexane). Anal. Calcd for C17H20O3: C, 74.97; H,
7.40. Found: C, 75.08; H, 7.41. GC–HRMS calcd for
C17H20O3: 272.1411. Found: 272.1411. GC–MS m/z: 272
(MC, 3), 244 (13), 182 (14), 129 (21), 115 (11), 99 (100), 86
(13), 55 (23). IR (CHCl3) cmK1: 1721. 1H NMR (300 MHz)
d: 1.44–1.70 (4H, m), 1.71–1.93 (2H, m), 2.14–2.23 (1H, m),
2.25–2.35 (2H, m), 2.83–2.97 (2H, m), 3.88–4.06 (4H, m),
6.91–6.96 (1H, m), 7.09–7.19 (3H, m), 9.27 (1H, d, JZ
2 Hz).
Compound 67-cis. Colorless prisms, mp 100–101 8C
(CH2Cl2–hexane). Anal. Calcd for C16H18O3: C, 74.39; H,
7.02. Found: C, 74.34; H, 6.93. GC–HRMS calcd for
C16H18O3: 258.1255. Found: 258.1261. GC–MS m/z: 258
(MC, 14), 215 (5), 112 (100), 99 (47), 86 (45). IR
(CHCl3) cmK1: 1678. 1H NMR (300 MHz) d: 1.56–1.86
(6H, m), 2.46 (1H, ddd, JZ10.5, 5.5, 5 Hz), 2.93 (1H, ddd,
JZ10, 5, 5 Hz), 3.00 (1H, dd, JZ16.5, 5.5 Hz), 3.11 (1H,
dd, JZ16.5, 10.5 Hz), 3.76–4.01 (4H, m), 7.26 (1H, br d, JZ
7.5 Hz), 7.30 (1H, br dd, JZ7.5, 7.5 Hz), 7.47 (1H, ddd, JZ
7.5, 7.5, 1.5 Hz), 8.03 (1H, dd, JZ7.5, 1.5 Hz).
Compound 69-trans. Colorless syrup. GC–HRMS calcd for
C17H20O3: 272.1411. Found: 272.1396. GC–MS m/z: 272
(MC, 29), 227 (33), 112 (31), 99 (100), 86 (26), 55 (30). IR
(CHCl3) cmK1: 1680. 1H NMR (300 MHz) d: 1.36–1.68
(3H, m), 1.74–1.87 (4H, m), 1.89 (1H, ddd, JZ12, 7.5,
2 Hz), 2.34 (1H, dddd, JZ15, 7, 2, 2 Hz), 2.85 (1H, ddd, JZ
17, 7, 1.5 Hz), 3.16–3.36 (1H, m), 3.46 (1H, br dd, JZ17,
11.5 Hz), 3.95–4.12 (4H, m), 7.20 (1H, br d, JZ7.5 Hz),
7.25 (1H, br dd, JZ7.5, 7.5 Hz), 7.36 (1H, ddd, JZ7.5, 7.5,
1.5 Hz), 7.72 (1H, dd, JZ7.5, 1.5 Hz).
4.5.2. (4aR*,9aS*)-3,4,4a,9,9a,10-Hexahydrospiro[anthra-
cene-1(2H),20-[1,3]dioxolan]-10-one (67-trans, Table 2,
run 1). Colorless prisms, mp 101–102 8C (CH2Cl2–hexane).
Anal. Calcd for C16H18O3: C, 74.39; H, 7.02. Found: C,
74.42; H, 6.96. GC–HRMS calcd for C16H18O3: 258.1255.
Found: 258.1258. GC–MS m/z: 258 (MC, 14), 215 (15), 112
1
(100), 99 (43), 86 (43). IR (CHCl3) cmK1: 1679. H NMR
Compound 69-cis. Colorless syrup. GC–HRMS calcd for
C17H20O3: 272.1411. Found: 272.1416. GC–MS m/z: 272
(MC, 25), 227 (29), 112 (30), 99 (100), 86 (29), 55 (25). IR
(CHCl3) cmK1: 1678. 1H NMR (300 MHz) d: 1.44–1.87
(6H, m), 1.94–2.09 (1H, m), 2.13–2.29 (2H, m), 2.89 (2H, t,
JZ6 Hz), 3.07 (1H, br dd, JZ5.5, 5.5, 5.5 Hz), 3.79–3.96
(4H, m), 7.17 (1H, br d, JZ7.5 Hz), 7.27 (1H, br dd, JZ7.5,
7.5 Hz), 7.36 (1H, ddd, JZ7.5, 7.5, 1.5 Hz), 7.62 (1H, br d,
JZ7.5 Hz).
(300 MHz) d: 1.27 (1H, dddd, JZ13.5, 13.5, 11.5, 4 Hz),
1.38 (1H, ddd, JZ13, 13, 4 Hz), 1.61 (1H, ddddd, JZ13.5,
13.5, 13.5, 4, 4 Hz), 1.78–1.90 (2H, m), 2.22 (1H, ddd, JZ
13, 10.5, 5.5 Hz), 2.43 (1H, br d, JZ13.5 Hz), 2.55 (1H,
ddd, JZ13, 11.5, 3.5 Hz), 2.96 (1H, dd, JZ16.5, 10.5 Hz),
3.03 (1H, dd, JZ16.5, 5.5 Hz), 4.01–4.10 (4H, m), 7.25
(1H, d, JZ7.5, 1.5 Hz), 7.29 (1H, dd, JZ7.5, 7.5 Hz), 7.46
(1H, ddd, JZ7.5, 7.5, 1.5 Hz), 8.01 (1H, dd, JZ7.5,
1.5 Hz).
4.5.3. Table 2, runs 5–8. The procedure of Table 2, run 7
was described as a representative of runs 5–8. In a similar
4.5.4. Table 2, runs 9 and 10. The procedure of Table 2, run
10 was described as a representative of runs 9 and 10. In the