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10 2-t-Butyldimethylsilyloxy-2-phenylacetohydroximoyl chloride
was prepared and used immediately without purification from 2-t-butyldimethylsilyloxy-2-phenylacetaldoxime
by NCS treatment. 2-t-Butyldimethyl-silyloxy-2-phenylacetaldoxime
was prepared from d-mandelic acid by esterification,
silylation, reduction by DIBAL-H, and aldoxime formation.
2-t-Butyldimethyl-silyloxy-2-phenylacetaldoxime: 1H
NMR (200 MHz, CDCl3): δ = 0.07 (d,
6 H, J = 15.5
Hz), 0.94 (s, 9 H), 3.73
(s, 1 H), 5.33 (d, 1 H, J = 7.1 Hz),
7.27-7.43 (m, 6 H). IR (NaCl): 3267, 2929, 2858, 1254,
1066, 838 cm-1.
11 To a solution of 1,5-hexadien-3-ol
(1.55 g, 15.7 mmol) in benzene (50 mL) was slowly added EtMgBr (16.0
mL, 1.5 M in THF) at 0 °C, and stirred for 30 min. Triphenylacetonitrile
oxide (3.00 g, 11.6 mmol) in benzene (10 mL) was added dropwise
to the reaction mixture at 0 °C. After stirring for 3 h,
the reaction mixture was poured into ice-water, extracted with ethyl
acetate (80 mL × 2), washed with aq 5% HCl
solution (100 mL) and brine, dried over MgSO4, and then
concentrated to give an oil. The oily residue was purified by flash
column chromatography (n-hex/EtOAc,
5/1) to afford syn-3 (R1 = triphenylmethyl)
as a pale yellow solid (2.84 g, 71%). 1H
NMR (200 MHz, CDCl3): δ = 2.30 (dd,
2 H, J = 6.3,
6.7 Hz), 2.86 (dd, 2 H, J = 2.6,
8.5 Hz), 3.50-3.59 (m, 1 H), 4.49-4.61 (m, 1 H), 5.10
(s, 1 H), 5.18 (d, 1 H, J = 4.2 Hz), 5.78-5.92
(m, 1 H) 7.22-7.41 (m, 15 H). MS: m/z (relative
intensity) = 383 (0.1) [M+ + 1],
312 (1), 244 (2), 226 (1), 215 (2), 165 (22), 77 (84), 51 (24),
41 (100). IR (NaCl): 3442, 2922, 2852, 1506, 1457, 701 cm-1.
HRMS calcd for C26H25NO2: 383.18852.
Found: 383.18829. Anal. Calcd for C26H25NO2:
C, 81.43; H, 6.57; N, 3.65. Found: C, 80.95; H, 6.70; N, 3.36. syn-3 (R1 = α-(t-Butyldimethylsilyloxy)benzyl): pale
yellow oil. 1H NMR (200 MHz, CDCl3): δ = 0.09
(d, 6 H, J = 1.7 Hz), 0.94 (s, 9 H), 2.45-2.72
(m, 2 H), 2.89-3.10 (m, 1 H), 3.40-3.56 (m, 1 H),
4.34-4.52 (m, 1 H), 5.01-5.17 (m, 2 H), 5.66-5.86
(m, 2 H), 7.27-7.38 (m, 5 H). MS: m/z (relative
intensity) = 346 (3) [M+ - CH3],
304 (100), 262 (2), 221 (14), 181 (12), 149 (14), 130 (7), 107 (13),
75 (42), 43 (13). IR (NaCl): 3430, 2930, 2857, 1468, 1255, 1092,
839 cm-1. Anal. Calcd for C20H31NO3Si:
C, 66.44; H, 8.64; N, 3.87. Found: C, 66.27; H, 8.86; N, 3.52.
12
Typical Procedure
of Iodoetheration (entry 1 in Table
[1]
): To
a solution of 5-(1-t-butyldimethylsilyloxy-3-butenyl)-3-triphenylmethyl-4,5-dihydroisoxazole
(4, 0.80 g, 1.61 mmol)
in dichloromethane (5 mL) was dropwise added iodine monochloride
(3.2 mL, 1.0 M in dichloromethane) at 0 °C and stirred
for 3 h at that temperature. The reaction mixture was washed with
aq 20% sodium bisulfite solution (10 mL × 2),
dried over MgSO4, and concentrated to give an oil. The
oily residue was purified by flash column chromatography (n-hex/EtOAc, 20/1)
to afford trans-5 and cis-5 as pale
yellow oils. trans-5 (R2 = TBDMS):
0.40 g (65%). 1H NMR (200 MHz, CDCl3): δ = 0.11
(d, 6 H, J = 3.9 Hz),
0.89 (s, 9 H), 1.85 (ddd, 1 H, J = 5.1,
9.3, 13.8 Hz), 2.12 (ddd, 1 H, J = 1.5,
6.6, 13.8 Hz), 2.59 (d, 2 H, J = 6.6
Hz), 3.26 (d, 2 H, J = 5.1
Hz), 4.19 (tdd, 1 H, J = 5.1,
6.6, 13.8 Hz), 4.27 (td, 1 H, J = 6.6,
13.8 Hz), 4.42-4.44 (m, 1 H). MS: m/z (relative
intensity) = 380 (0.5) [M+ + 1],
366 (1), 324 (25), 283 (8), 255 (9), 198 (6), 185 (9), 156 (100),
128 (15), 98 (16), 73 (21). IR (NaCl): 2877, 2253 cm-1.
Anal. Calcd for C13H24INO2Si: C,
40.95; H, 6.34; N, 3.67. Found: C, 40.96; H, 6.11; N, 3.77. cis-5 (R2 = TBDMS):
0.06 g (11%). 1H NMR (200 MHz, CDCl3): δ = 0.11
(d, 6 H, J = 3.2 Hz),
0.90 (s, 9 H), 1.99 (ddd, 1 H, J = 3.0,
4.5, 13.8 Hz), 2.29 (ddd, 1 H, J = 6.0,
7.8, 13.8 Hz), 2.61 (d, 2 H, J = 6.0
Hz), 3.26-3.32 (m, 2 H), 4.10-4.20 (m, 2 H), 4.36-4.40
(m, 1 H). trans-5 (R2 = TBDPS): 1H
NMR (200 MHz, CDCl3): δ = 1.09 (s,
9 H), 1.61 (ddd, 1 H, J = 5.1,
8.6, 16.7 Hz), 2.04 (ddd, 1 H, J = 2.5,
8.5, 16.7 Hz), 2.63-2.68 (m, 2 H), 3.17 (d, 2 H, J = 5.1 Hz),
4.18-4.31 (m, 2 H), 4.47-4.53 (m, 1 H), 7.37-7.52
(m, 6 H), 7.63-7.70 (m, 1 H). MS: m/z (relative intensity) = 405
(0.5) [M+ - CNCH2-C(CH3)3],
339 (1), 322 (9), 304 (1), 280 (8), 244 (8), 199 (100), 181 (15),
161 (11), 135 (21). IR (NaCl): 2878, 2255 cm-1.
Anal. Calcd for C23H28INO2Si: C,
54.65; H, 5.58; N, 2.77. Found: C, 55.01; H, 5.59; N, 2.77. cis-5 (R2 = TBDPS): 1H
NMR (200 MHz, CDCl3): δ = 1.10 (s,
9 H), 1.87 (ddd, 1 H, J = 5.5,
7.2, 13.5 Hz), 2.08 (ddd, 1 H, J = 6.7,
13.5, 13.2 Hz), 2.48-2.72 (m, 2 H), 3.22-3.34
(m, 2 H), 3.91-4.09 (m, 2 H), 4.48-4.54 (m, 1 H),
7.36-7.48 (m, 6 H), 7.61-7.68 (m, 1 H). trans-5 (R2 = MPM): 1H
NMR (200 MHz, CDCl3): δ = 1.78 (ddd,
1 H, J = 4.7,
8.2, 16.1 Hz), 2.37 (ddd, 1 H, J = 1.6,
5.9, 16.1 Hz), 2.55-2.77 (m, 2 H), 3.27 (d, 2 H, J = 4.7 Hz),
3.81 (s, 3 H), 4.14-4.26 (m, 2 H), 4.33-4.45 (m,
2 H), 4.58 (d, 1 H, J = 10.2
Hz), 6.89 (d, 2 H, J = 9.7
Hz), 7.28 (d, 2 H, J = 9.2 Hz).
MS: m/z (relative intensity) = 388
(78) [M+ - 1], 371 (19),
353 (13), 327 (7), 298 (10), 281 (12), 247 (15), 172 (55), 127 (100),
101 (10), 43 (92). IR (NaCl): 2878, 2251 cm-1.
HRMS calcd for C15H18INO3: 387.03314.
Found: 387.03452. Anal. Calcd for C15H18INO3:
C, 46.53; H, 4.69; N, 3.62. Found: C, 46.26; H, 4.79; N, 3.57. trans-5 (R2 = MEM): 1H
NMR (200 MHz, CDCl3): δ = 1.87-1.91 (m,
1 H), 2.32-2.45 (m, 1 H), 2.66-2.77 (m, 2 H),
3.23-3.29 (m, 2 H), 3.39 (s, 3 H), 3.57-3.64 (m,
2 H), 3.72-3.81 (m, 2 H), 4.14-4.19 (m, 2 H),
4.39-4.45 (m, 1 H), 4.79-4.85 (m, 2 H). MS: m/z (relative intensity) = 354(4) [M+ + 1],
296 (1), 281 (4), 249 (4), 209 (4), 169 (3), 141 (5), 122 (25),
105 (10), 89 (91), 59 (100). IR (NaCl): 2880, 2254 cm-1.
Anal. Calcd for C11H18INO4: C,
37.20; H, 5.11; N, 3.94. Found: C, 37.05; H, 5.20; N, 3.81. trans-5 (R2 = MEM): 1H
NMR (200 MHz, CDCl3): δ = 1.86 (ddd,
1 H, J = 4.5,
9.1, 13.2 Hz), 2.38 (ddd, 1 H, J = 1.6,
5.9, 13.2 Hz), 2.62-2.74 (m, 2 H), 3.29 (d, 2 H, J = 4.5 Hz),
3.42 (s, 3 H), 4.15-4.28 (m, 1 H), 4.36-4.44 (m, 2
H), 4.66-4.76 (m, 2 H). MS: m/z (relative
intensity) = 310 (2) [M+ + 1],
281 (4), 249 (10), 197 (17), 169 (13), 122 (26), 108 (19), 69 (25),
45 (100), 29 (11). IR (NaCl): 2879, 2254 cm-1.
HRMS calcd for C9H14INO3: 311.00184.
Found: 311.00266. Anal. Calcd for C9H14INO3:
C, 34.74; H, 4.54; N, 4.50. Found: C, 34.53; H, 4.43; N, 4.78.
13
trans-5 (R2 = H): 1H
NMR (200 MHz, CDCl3): δ = 1.97 (dd, 1
H, J = 7.1,
21.1 Hz), 2.26 (dd, 1 H, J = 4.9,
17.3 Hz), 2.71 (d, 2 H, J = 7.1
Hz), 3.29 (d, 2 H, J = 4.9
Hz), 4.23-4.37 (m, 2 H), 4.47-4.61 (m, 1 H), 4.35-4.42
(m, 1 H). MS: m/z (relative
intensity) = 267 (5) [M+],
197 (8), 169 (5), 140 (100), 126 (73), 99 (8), 82 (52), 71 (19).
IR (NaCl): 2878, 2251 cm-1. HRMS calcd
for C7H10INO2: 266.97605. Found: 266.97563.
Anal. Calcd for C7H10INO2: C, 31.48;
H, 3.77; N, 5.24. Found: C, 31.84; H, 3.59; N, 5.45. cis-5 (R2 = H): 1H
NMR (200 MHz, CDCl3): δ = 1.78 (dd,
1 H, J = 5.7,
23.1 Hz), 2.25 (dd, 1 H, J = 5.5,
14.3 Hz), 2.63 (d, 2 H, J = 5.7 Hz),
3.31 (d, 2 H, J = 5.5
Hz), 4.25-4.35 (m, 2 H), 4.49-4.61 (m, 1 H). IR
(NaCl): 3460, 2925, 2252, 1082 cm-1.
HRMS calcd for C7H10INO2: 266.97605.
Found: 266.97634.