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T. Tanaka et al. / Tetrahedron 61 (2005) 6726–6742
3.5 mmol) at K78 to 0 8C for 6 h: colorless oil; [a]2D6C45.5
procedure for the allyltitanium-mediated ring-opening
reaction, epoxide 52 (108 mg, 0.50 mmol) was converted
into 60 (63 mg, 49% yield) by the reaction with allylmag-
nesium chloride (2.0 M in THF; 1.75 mL, 3.5 mmol) and
chlorotitanium triphenoxide (0.5 M in THF; 7.0 mL,
3.5 mmol) at K78 to 0 8C for 6 h: colorless oil; [a]2D6C
18.4 (c 1.02, CHCl3); IR (KBr) cmK1 3486 (OH); 1H NMR
(500 MHz, CDCl3) d 0.85 (t, JZ6.9 Hz, 3H, CMe), 0.97 (s,
3H, CMe), 1.16–1.46 (m, 10H), 2.22–2.36 (m, 2H, 3-CH2),
3.38 (s, 3H, OMe), 3.46–3.58 (m, 3H, 5-H and 10-CH2), 4.63
(s, 2H, OCH2O), 5.10–5.13 (m, 2H, 1-CH2), 5.85–5.93 (m,
1H, 2-H); 13C NMR (75 MHz, CDCl3) d 14.8, 15.8, 22.9,
24.2, 30.4, 31.0, 34.1, 35.9, 41.1, 55.5, 72.7, 76.7, 98.8,
120.2, 130.6; MS (FAB) m/z (%): 259 (MHC, 34), 183
(100); HRMS (FAB) calcd for C15H31O3 (MHC): 259.2273;
found: 259.2286.
1
(c 1.00, CHCl3); IR (KBr) cmK1 3483 (OH); H NMR
(500 MHz, CDCl3) d 0.92 (t, JZ6.4 Hz, 3H, CMe), 1.13
(q, JZ6.4 Hz, 2H, CH2Me), 2.18 (dd, JZ14.0, 7.9 Hz, 1H,
4-CHH), 2.20–2.32 (m, 1H, 4-CHH), 2.52 (d, JZ4.9 Hz,
1H, OH), 2.64 (dd, JZ13.4, 10.4 Hz, 1H, 1-CHH), 2.82 (dd,
JZ13.4, 1.2 Hz, 1H, 1-CHH), 3.40–3.56 (m, 2H, 10-CH2),
3.64–3.68 (m, 1H, 2-H), 4.47 (s, 2H, PhCH2), 5.12–5.16
(m, 2H, 6-CH2), 5.84–5.93 (m, 1H, 5-H), 7.12–7.40 (m,
10H, Ph); 13C NMR (75 MHz, CDCl3) d 12.3, 22.5, 37.1,
39.0, 41.9, 70.7, 75.9, 78.4, 117.1, 125.9, 127.7 (2C), 127.9
(2C), 130.7 (2C), 131.0 (2C), 138.3, 138.4, 138.6 (2C); MS
(FAB) m/z (%): 347 (MNaC, 48), 126 (100); HRMS (FAB)
calcd for C22H28NaO2 (MNaC): 347.1987; found:
347.1990.
4.2.22. (2R,3S)-3-Ethyl-3-(methoxymethoxymethyl)-1-
phenylhex-5-en-2-ol (58) (Table 3, entry 5). By the general
procedure for the allyltitanium-mediated ring-opening
reaction, epoxide 50 (118 mg, 0.50 mmol) was converted
into 58 (58 mg, 42% yield) by the reaction with allylmag-
nesium chloride (2.0 M in THF; 1.75 mL, 3.5 mmol) and
chlorotitanium triphenoxide (0.5 M in THF; 7.0 mL,
3.5 mmol) at K78 to 0 8C for 3 h: colorless oil; [a]2D4C
12.6 (c 0.96, CHCl3); IR (KBr) cmK1 3546 (OH); 1H NMR
(500 MHz, CDCl3) d 0.91 (t, JZ6.4 Hz, 3H, CMe), 1.05
(q, JZ6.4 Hz, 2H, 3-CH2Me), 2.14 (dd, JZ14.0, 7.9 Hz,
1H, 4-CHH), 2.20–2.29 (m, 1H, 4-CHH), 2.43 (d, JZ
4.9 Hz, 1H, OH), 2.50 (dd, JZ13.4, 10.4 Hz, 1H, 1-CHH),
2.90 (dd, JZ13.4, 1.2 Hz, 1H, 1-CHH), 3.28 (s, 3H, OMe),
3.43–3.51 (m, 2H, 10-CH2), 3.69–3.76 (m, 1H, 2-H), 4.61
(s, 2H, OCH2O), 5.10–5.14 (m, 2H, 6-CH2), 5.80–5.93 (m,
1H, 5-H), 7.25–7.34 (m, 5H, Ph); 13C NMR (75 MHz,
CDCl3) d 14.2, 22.5, 37.6, 38.9, 41.6, 56.3, 72.0, 78.4, 96.0,
117.4, 126.6, 129.3 (2C), 128.9 (2C), 136.1, 138.6;
MS (FAB) m/z (%): 279 (MHC, 30), 184 (100); HRMS
(FAB) calcd for C17H27O3 (MHC): 279.1960; found:
279.1952.
4.2.25. (4S,5R)-4-(Benzyloxymethyl)-4-methylundec-1-
en-5-ol (61) (Table 3, entry 8). By the general procedure
for the allyltitanium-mediated ring-opening reaction, epox-
ide 53 (131 mg, 0.50 mmol) was converted into 61 (50 mg,
33% yield) by the reaction with allylmagnesium chloride
(2.0 M in THF; 1.75 mL, 3.5 mmol) and chlorotitanium
triphenoxide (0.5 M in THF; 7.0 mL, 3.5 mmol) at K78 to
0 8C for 8 h: colorless oil; [a]2D4C29.0 (c 0.90, CHCl3); IR
(KBr) cmK1 3523 (OH); 1H NMR (500 MHz, CDCl3) d 0.88
(t, JZ6.9 Hz, 3H, CMe), 0.95 (s, 3H, CMe), 1.12–1.34 (m,
10H), 2.18–2.26 (m, 2H, 3-CH2), 2.40 (d, JZ5.4 Hz, 1H,
OH), 3.20 (dd, JZ13.4, 5.4 Hz, 1H, 5-H), 3.46 (s, 2H,
10-CH2), 4.50 (s, 2H, PhCH2), 5.06–5.12 (m, 2H, 1-CH2),
5.78–5.83 (m, 1H, 2-H), 7.22–7.36 (m, 5H, Ph); 13C NMR
(75 MHz, CDCl3) d 14.6, 15.3, 22.2, 24.8, 30.2, 30.4, 34.7,
36.0, 40.6, 68.6, 74.2, 77.4, 117.9, 127.04, 127.07, 130.1
(2C), 132.6 (2C), 136.4; MS (FAB) m/z (%): 305 (MHC,
40), 91 (100); HRMS (FAB) calcd for C20H33O2 (MHC):
305.2481; found: 305.2476.
4.3. Preparation of epoxides
4.2.23. (2R,3R)-3-Ethyl-3-(methoxymethoxymethyl)-1-
phenylhex-5-en-2-ol (59) (Table 3, entry 6). By the general
procedure for the allyltitanium-mediated ring-opening
reaction, epoxide 51 (118 mg, 0.50 mmol) was converted
into 59 (52 mg, 37% yield) by the reaction with allylmag-
nesium chloride (2.0 M in THF; 1.75 mL, 3.5 mmol) and
chlorotitanium triphenoxide (0.5 M in THF; 7.0 mL,
3.5 mmol) at K78 to 0 8C for 3 h: colorless oil; [a]2D8C
34.4 (c 0.90, CHCl3); IR (KBr) cmK1 3560 (OH); 1H NMR
(500 MHz, CDCl3) d 0.93 (t, JZ6.4 Hz, 3H, CMe), 1.08
(q, JZ6.4 Hz, 2H, 3-CH2Me), 2.20 (dd, JZ14.0, 7.9 Hz,
1H, 4-CHH), 2.29–2.33 (m, 1H, 4-CHH), 2.45 (d, JZ
4.9 Hz, 1H, OH), 2.57 (dd, JZ13.4, 10.4 Hz, 1H, 1-CHH),
2.93 (dd, JZ13.4, 10.2 Hz, 1H, 1-CHH), 3.38 (s, 3H, OMe),
3.46–3.58 (m, 2H, 1 -CH2), 3.71–3.77 (m, 1H, 2-H), 4.61 (s,
2H, OCH2O), 5.10–5.13 (m, 2H, 6-CH2), 5.86–5.92 (m, 1H,
5-H), 7.23–7.30 (m, 5H, Ph); 13C NMR (75 MHz, CDCl3) d
14.3, 22.7, 37.8, 38.9, 41.0, 56.1, 72.3, 77.9, 95.9, 117.3,
126.6, 129.0 (2C), 129.1 (2C), 136.1, 138.7; MS (FAB) m/z
(%): 279 (MHC, 26), 184 (100); HRMS (FAB) calcd for
C17H27O3 (MHC): 279.1960; found: 279.1971.
4.3.1. (6)-9-(Oxiran-2-yl)-1-pyrrolidinylnonan-1-one
(3). To a stirred solution of 1-pyrrolidinylundec-10-en-1-
one 6226 (2.50 g, 10.5 mmol) in CH2Cl2 (20 mL) was added
dropwise a solution of 75% m-CPBA (3.08 g, 13.4 mmol) in
CH2Cl2 (30 mL) at 0 8C, and the mixture was stirred for 4 h
at room temperature. Saturated Na2S2O3 was added to the
mixture and stirring was continued for 30 min. Organic
layer was separated and washed with saturated NaHCO3
(!2), water, and brine, and dried over MgSO4. Concen-
tration of the filtrate under reduced pressure gave an oily
residue, which was purified by column chromatography
over silica gel with hexane–EtOAc (3:2) to give 3 (1.43 g,
54% yield) as a colorless oil; IR (KBr) cmK1 1643 (C]O);
1H NMR (300 MHz, CDCl3) d 1.25–1.66 (m, 14H, 7!
CH2), 1.80–2.00 (m, 4H, 30-CH2 and 40-CH2), 2.22–2.28 (m,
2H, 2-CH2), 2.45–2.48 (m, 1H, OCHH), 2.73–2.76 (m, 1H,
OCHH), 2.88–2.93 (m, 1H, OCH), 3.39–3.48 (m, 4H,
20-CH2 and 50-CH2); 13C NMR (75 MHz, CDCl3) d 24.4,
24.9, 25.9, 26.1, 29.31 (2C), 29.35, 29.4, 32.4, 34.8, 45.5,
46.6, 47.1, 52.4, 171.8; MS (FAB) m/z (%): 254 (MHC,
4.2.24. (4S,5R)-4-(Methoxymethoxymethyl)-4-methyl-
undec-1-en-5-ol (60) (Table 3, entry 7). By the general