Y. J. Lee et al. / Tetrahedron 61 (2005) 1987–2001
1999
(hexane/EtOAc, 1:3) to give the title compound 48 (0.24 g,
77%) and conpound 49 (24 mg, 8%) as a colorless oil,
respectively. Compound 48: RfZ0.28 (hexane/EtOAc, 1:3);
[a]DZC37.5 (c 1.7, CHCl3); 1H NMR (250 MHz, CDCl3)
d 1.73–1.84 (m, 1H), 1.89–2.05 (m, 2H), 2.17–2.29 (m, 1H),
2.55 (m, 2H), 3.53–3.79 (m, 3H), 4.04 (s, 1H), 4.63–4.68
(dd, JZ8.5, 3.8 Hz, 1H), 5.65–5.71 (m, 1H), 5.80–5.86 (m,
1H), 7.32–7.39 (m, 5H); 13C NMR (63 MHz, CDCl3) d 22.1,
23.8, 66.3, 67.4, 74.4, 80.5, 127.0, 127.4, 128.6, 128.9,
130.9, 138.8; IR (CHCl3, film) 3421, 1453, 1229, 1111,
1051 cmK1. Anal. calcd for C14H18O3: C, 71.77; H, 7.74.
Found: C, 71.75; H, 7.75. Compound 49: RfZ0.35 (hexane/
EtOAc, 1:3); [a]DZK164.9 (c 2.5, CHCl3); 1H NMR
(250 MHz, CDCl3) d 1.26–2.15 (m, 4H), 3.23 (br s, 2H),
3.54–3.63 (m, 1H), 3-65-3.76 (m, 2H), 4.36 (m, 1H), 4.67–
4.72 (dd, JZ8.3, 4.3 Hz, 1H), 5.75–5.88 (m, 2H), 7.28–7.37
(m, 5H); 13C NMR (63 MHz, CDCl3) d 24.3, 24.4, 64.2,
67.8, 76.2, 81.3, 126.7, 126.9, 128.2, 128.6, 131.6, 139.4; IR
(CHCl3, film) 3375, 1453, 1433, 1104, 1058 cmK1. Anal.
calcd for C14H18O3: C, 71.77; H, 7.74. Found: C, 71.73; H,
7.70.
13C NMR (63 MHz, CDCl3) d 22.0, 23.9, 35.8, 66.0, 74.6,
79.4, 126.7, 127.0, 127.2, 128.5, 128.9, 129.2, 130.9, 132.5,
141.5; IR (CHCl3, film) 3421, 1098 cmK1. Anal. calcd for
C20H22O2Se: C, 64.34; H, 5.94. Found: C, 64.34; H, 5.95.
4.1.40. (1S,2R,10S)-Benzoic acid 2-(1-phenyl-2-phenyl-
selanyl-ethoxy)-cyclohex-3-enyl-ester (52). To a solution
of compound 51 (87 mg, 0.2 mmol) in DMF (5 mL) at 0 8C
was added NaH (60%, 12 mg, 0.3 mmol). After stirring for
30 min at 0 8C, benzyl bromide (47 mg, 0.3 mmol) was
added. The resulting solution was stirred for 12 h at 0 8C,
diluted with EtOAc and washed with saturated NH4Cl
solution several times. The organic layer was dried over
MgSO4 and concentrated. The residue was purified by flash
column chromatography (hexane/EtOAc, 10:1) to give the
title compound 52 (86 mg, 79%) as a yellow oil. RfZ0.38
1
(hexane/EtOAc, 10:1); [a]DZK26.8 (c 0.5, CHCl3); H
NMR (250 MHz, CDCl3) d 1.66–1.71 (m, 1H), 1.94–2.10
(m, 2H), 2.37–2.40 (m, 1H), 3.11–3.15 (dd, JZ12.3, 4.8 Hz,
1H), 3.33-3.39 (dd, JZ12.2, 8.4 Hz, 1H), 3.54–3.56 (m,
1H), 4.00 (m, 1H), 4.50–4.53 (d, JZ6.1 Hz, 1H), 4.61–4.64
(d, JZ6.1 Hz, 1H), 4.65–4.66 (m, 1H), 5.65–5.67 (m, 1H),
5.78–5.80 (m, 1H), 7.22–7.48 (m, 15H); 13C NMR
(63 MHz, CDCl3) d 22.5, 24.2, 36.0, 71.7, 73.4, 74.2,
79.4, 126.0, 126.8, 127.1, 127.4, 127.8, 128.2, 128.3, 128.6,
129.1, 130.8, 131.3, 132.4, 139.4, 142.0; IR (CHCl3, film)
4.1.38. (1S,2R,10S)-Toluene-4-sulfonic acid 2-(6-
hydroxy-cyclohex-2-enyloxy)-2-phenyl-ethyl ester (50).
To a solution of compound 48 (118 mg, 0.50 mmol) and
DMAP (19 mg, 0.16 mmol) in CH2Cl2 (20 mL) and TEA
(10 mL) at 0 8C was added TsCl (96 mg, 0.50 mmol). After
stirring 1 h at 0 8C, the reaction mixture was diluted with
CH2Cl2. The organic layer was washed with saturated
NH4Cl solution several times, dried over MgSO4 and
concentrated. The residue was purified by flash column
chromatography (hexane/EtOAc, 2:1) to give the title
compound 50 (183 mg, 93%) as a colorless oil. RfZ0.33
(hexane/EtOAc, 2:1); [a]DZC63.4 (c 2.5, CHCl3); 1H
NMR (250 MHz, CDCl3) d 1.63–1.76 (m, 1H), 1.85–2.00
(m, 2H), 2.17–2.26 (m, 1H), 2.28–2.31 (d, JZ5.5 Hz, 1H),
2.44 (s, 2H), 3.48-3.55 (m, 1H), 3.99–4.00 (m, 1H), 4.04–
4.16 (m, 2H), 4.74–4.79 (dd, JZ7.4, 4.5 Hz, 1H), 5.61–5.67
(m, 1H), 5.78–5.83 (m, 1H), 7.26–7.39 (m, 7H), 7.72–7.75
(m, 2H); 13C NMR (63 MHz, CDCl3) d 21.8, 22.1, 23.5,
66.0, 72.9, 75.0, 77.2, 127.0, 128.0, 129.0, 129.1, 130.0,
131.0, 133.1, 137.2, 145.0; IR (CHCl3, film) 3421, 1355,
1177, 1098 cmK1. Anal. calcd for C21H24O5S: C, 64.93; H,
6.23; S, 8.25. Found: C, 64.84; H, 6.24; S, 8.71.
1578, 1480, 1453, 1104 cmK1
. HRMS calcd for
C27H28O2Se (M)C: m/z 464.1255. Found: 464.1252.
4.1.41. (1S,6S)-6-Benzyloxy-cyclohex-2-enol (53). Com-
pound 52 (110 mg, 0.2 mmol) was subjected to the same
reaction conditions as that for the preparation of 42 from 41.
The reaction mixture was purified by flash column
chromatography (hexane/EtOAc, 7:1) to give the title
compound 53 (30 mg, 62%) as a yellow oil. RfZ0.35
1
(hexane/EtOAc, 3:1); [a]DZK120.7 (c 1.5, CHCl3); H
NMR (250 MHz, CDCl3) d 1.69–1.71 (m, 1H), 1.88–2.03
(m, 2H), 2.24–2.27 (m, 1H), 2.51–2.52 (d, JZ5.1 Hz, 1H),
3.95 (m, 2H), 4.63–4.65 (d, JZ11.7 Hz, 1H), 4.68–4.71 (d,
JZ11.7 Hz, 1H), 5.71–5.73 (m, 1H), 5.88–5.90 (m, 1H),
7.30–7.36 (m, 5H); 13C NMR (63 MHz, CDCl3) d 23.1,
26.6, 67.0, 71.1, 73.9, 124.8, 127.9, 128.6, 131.9, 138.5; IR
(CHCl3, film) 3430, 1216, 1074 cmK1. HRMS calcd for
C13H16O2 (M)C: m/z 204.1150. Found: 204.1168.
4.1.39. (1S,2R,10S)-2-(1-Phenyl-2-phenylselanyl-ethoxy)-
cyclohex-3-enol (51). To a solution of compound 50
(184 mg, 0.5 mmol) in EtOH (10 mL) at rt was added
NaBH4 (54 mg, 1.4 mmol) and DPDS (222 mg, 0.7 mmol).
After stirring for 3 h at 70 8C, the reaction mixture was
quenched with water and concentrated to remove EtOH.
The aqueous solution was neutralized with saturated NH4Cl
solution, and extracted with CH2Cl2. The organic layer was
washed with brine, dried over MgSO4 and concentrated.
The residue was purified by flash column chromatography
(hexane/EtOAc, 3:1) to give the title compound 51 (160 mg,
90%) as a colorless oil. RfZ0.55 (hexane/EtOAc, 3:1);
[a]DZC29.5 (c 3.0, CHCl3); 1H NMR (250 MHz, CDCl3)
d 1.64–1.75 (m, 1H), 1.83–1.98 (m, 2H), 2.23–2.35 (m, 1H),
2.38–2.39 (d, JZ4.0 Hz, 1H), 3.09–3.15 (dd, JZ12.5,
4.5 Hz, 1H), 3.32–3.41 (dd, JZ12.5, 8.8 Hz, 1H), 3.43–3.50
(m, 1H), 3.96 (s, 1H), 4.68–4.73 (dd, JZ8.8, 4.5 Hz, 1H),
5.61–5.67 (m, 1H), 5.77–5.82 (m, 1H), 7.23–7.51 (m, 10H);
4.1.42. (1R,6S)-(6-Benzyloxy-cyclohex-2-enyloxy)-tert-
butyl-diphenyl-silane (54). A solution of compound 53
(40 mg, 0.2 mmol) and TBDPSCl (82 mg, 0.3 mmol) in the
presence of DMAP (7 mg, 0.06 mmol) and imidazole
(40 mg, 0.6 mmol) in DMF (5 mL) was stirred for 12 h at
80 8C. The reaction mixture was allowed to rt, dilute with
EtOAc and washed with saturated NH4Cl solution several
times. The organic layer was dried over MgSO4 and
concentrated. The residue was purified by flash column
chromatography (hexane/EtOAc, 15:1) to give the title
compound 54 (83 mg, 96%) as a colorless oil: RfZ0.50
1
(hexane/EtOAc, 15:1); [a]DZK55.2 (c 4.5, CHCl3); H
NMR (250 MHz, CDCl3) d 1.10 (s, 9H), 1.42–1.49 (m, 1H),
1.70–1.81 (m, 1H), 1.91–2.17 (m, 2H), 3.81 3.84 (t, JZ
3.5 Hz, 1H), 3.94–4.00 (dt, JdZ10.5 Hz, JtZ3.1 Hz, 1H),
4.62–4.67 (d, JZ12.2 Hz, 1H), 4.77–4.82 (d, JZ12.2 Hz,
1H), 5.53–5.75 (m, 2H), 7.20–7.43 (m, 11H), 7.70–7.74 (m,
4H); 13C NMR (63 MHz, CDCl3) d 19.4, 25.0, 26.3, 27.2,