L. Tietze et al.
FULL PAPER
CDCl3): d 14.06, 14.49, 15.99, 16.82, 22.59, 23.57, 29.75, 31.75, 36.44, 38.58,
J 8.0 Hz, 1H), 7.19 ± 7.39 (m, 5H); 13C NMR (50 MHz, CDCl3): d 16.44,
1
1
41.11, 51.41, 73.63, 81.28, 115.90 (q, JCF 288 Hz), 117.57, 127.24, 127.83,
17.29, 27.02, 38.60, 43.91, 46.12, 51.59, 60.59, 75.53, 77.81, 115.77 (q, JCF
2
1
2
128.21, 134.35, 140.68, 156.52 (q, JCF 36 Hz); IR (KBr): nÄ 3312 cm
,
290 Hz), 118.48, 125.88, 126.68, 127.81, 133.54, 140.77, 156.37 (q, JCF
3108, 3078, 3032, 2960, 2934, 2872, 1726, 1704, 1566, 1210, 1184, 1166, 1050,
914, 760, 702; MS (70 eV, CI(NH3)): m/z (%) 445 (100); C24H36F3NO2
(427.6): calcd C 67.40, H 8.49; found C 67.46, H 8.38.
37 Hz); IR (film): nÄ 3318 cm 1, 3080, 2978, 2938, 2876, 1724, 1712, 1554,
1456, 1286, 1210, 1166, 1056, 704; MS (70 eV, FD): m/z (%) 402 (2), 303
(4), 230 (100), 197 (83), 107 (61), 95 (95), 57 (45), 41 (17).
General procedure 2: Synthesis of the homoallylic alcohols 5 from 4 by
reductive removal of the chiral auxiliary: Condensed ammonia (40 mL)
and afterwards solid sodium (2.5 equiv) was added at 788C to a solution
of the homoallylic ether 4 (0.5 mmol) in THF (1 mL) with vigorous stirring.
When the solution turned deep blue, the reaction was quenched by adding
methanol (5 mL). The mixture was concentrated, the residue dissolved in
Et2O (20 mL), and the obtained solution washed with brine and dried over
Na2SO4. The solvent was evaporated in vacuo and the residue purified by
column chromatography on silica gel with ethyl ether/pentane (1/10) as the
eluent to give the homoallylic alcohol 5.
(3S,1'S,2'S)-O-Benzoyl-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-pro-
poxy)-hex-5-en-1-ol (8c): Reaction of ketone 7c (384 mg, 2.00 mmol) with
ent-2 (319 mg, 1.00 mmol) according to general procedure 1 for 4 d gave the
homoallylic ether 8c (130 mg, 0.28 mmol, 28%) as a colorless oil. [a]D20
1
20.88 (c 1, CHCl3); H NMR (200 MHz, CDCl3): d 1.08 (s, 3H), 1.19
(d, J 6.5 Hz, 3H), 1.78 ± 2.08 (m, 2H), 2.41 (d, J 7.5 Hz, 2H), 4.03 ± 4.23
(m, 1H), 4.26 ± 4.54 (m, 2H), 4.65 (d, J 4.0 Hz, 1H), 5.14 (d, J 11 Hz,
1H), 5.16 (d, J 16 Hz, 1H), 5.86 (ddd, J 16, 11, 7.5 Hz, 1H), 6.43 (d, J
8.0 Hz, 1H), 7.44 (dd, J 7.5, 7.5 Hz, 2H), 7.56 (t, J 7.5 Hz, 1H), 8.02 (d,
J 7.5 Hz, 2H); 13C NMR (50 MHz, CDCl3): d 16.54, 23.96, 38.13, 43.90,
1
51.59, 61.15, 74.41, 77.89, 115.81 (q, JCF 288 Hz), 118.69, 126.66, 127.92,
(3S)-3-Methylhex-5-en-3-ol (5a): Reaction of 4a (172 mg, 0.50 mmol) with
sodium (29 mg, 1.25 mmol) according to general procedure 2 gave 5a
(49 mg, 0.38 mmol, 76%). [a]2D0 8.78 (c 1, CHCl3); 1H NMR
(200 MHz, CDCl3): d 0.96 (t, J 7.0 Hz, 3H), 1.15 (s, 3H), 1.49 (q, J
7.0 Hz, 2H), 1.60 (brs, 1H), 2.22 (d, J 7.0 Hz, 2H), 5.05 ± 5.20 (m, 2H),
5.77 ± 5.99 (m, 1H); 13C NMR (50 MHz, CDCl3): d 8.16, 26.14, 34.23,
45.75, 72.33, 118.50, 134.11; IR (film): nÄ 3382 cm 1, 3076, 2932, 2862, 1462,
1378, 1262, 1126, 1056, 1032, 1000, 912, 734; C7H14O (114.2): calcd C 73.63,
H 12.36; found C 73.55, H 12.21.
128.30, 128.35, 129.46, 132.89, 133.46, 140.74, 156.47 (q, 2JCF 37 Hz, C O),
166.49; IR (film): nÄ 3318 cm 1, 3072, 2978, 2936, 1720, 1706, 1552, 1454,
1276, 1208, 1178, 1070, 712; MS (70 eV, FD): m/z (%) 422 (2), 323 (4), 230
(100), 217 (83), 105 (80), 95 (97), 77 (47); C25H28F3NO4 (463.5): calcd C
64.78, H 6.09; found C 64.88, H 6.26.
(3S,1'S,2'S)-O-p-Methoxybenzoyl-3-methyl-3-(1'-phenyl-2'-trifluoroacet-
amido-1'-propoxy)-hex-5-en-1-ol (8e): Reaction of ketone 7e (444 mg,
2.00 mmol) with ent-2 (319 mg, 1.00 mmol) according to general procedure
1 for 4 d gave the homoallylic ether 8e (155 mg, 0.31 mmol, 31%) as a
colorless oil. 1H NMR (200 MHz, CDCl3): d 1.06 (s, 3H), 1.18 (d, J
6.5 Hz, 3H), 1.77 ± 2.04 (mc, 2H), 2.39 (d, J 7.5 Hz, 2H), 3.85 (s, 3H),
4.02 ± 4.22 (m, 1H), 4.22 ± 4.50 (m, 2H), 4.65 (d, J 4.5 Hz, 1H), 5.14 (d,
J 12 Hz, 1H), 5.16 (d, J 16 Hz, 1H), 5.85 (ddd, J 16, 12, 7.5 Hz, 1H),
6.53 (brd, J 8.0 Hz, 1H), 6.90 (d, J 8.5 Hz, 2H), 7.19 ± 7.43 (m, 5H), 7.94
(d, J 8.5 Hz, 2H); 13C NMR (50 MHz, CDCl3): d 16.52, 23.93, 38.14,
(3S)-3-Methyl-1-phenylhex-5-en-3-ol (5b): Reaction of 4b (210 mg,
0.50 mmol) with sodium (29 mg, 1.25 mmol) according to general proce-
dure 2 gave 5b (88 mg, 0.46 mmol, 92%). [a]D20
58.08 (c 1, CHCl3); 1H
NMR (200 MHz, CDCl3): d 1.16 (s, 3H), 1.58 (brs, 1H), 1.55 ± 1.79 (m,
2H), 2.30 (d, J 7.0 Hz, 2H), 2.60 ± 2.82 (m, 2H), 5.07 ± 5.22 (m, 2H), 5.89
(ddd, J 16, 10, 7.0 Hz, 1H), 7.12 ± 7.38 (m, 5H); 13C NMR (50 MHz,
CDCl3): d 26.73, 30.25, 43.70, 46.43, 72.03, 119.03, 125.65, 128.34, 128.40,
133.77, 142.51; IR (film): nÄ 3344 cm 1, 3080, 3066, 3028, 2958, 2928, 2872,
1458, 1380, 1216, 1180, 1116, 1062, 1030, 994, 912, 730, 694; MS (70 eV, EI):
m/z (%) 191 (2), 149 (39), 131 (16), 105 (8), 91 (100), 43 (20); C7H14O
(190.3): calcd C 82.06, H 9.53; found C 82.00, H 9.45.
1
43.87, 51.60, 55.35, 60.82, 74.40, 77.87, 113.53, 115.84 (q, JCF 288 Hz),
118.61, 122.57, 126.66, 127.89, 128.32, 131.49, 133.52, 140.81, 156.47 (q,
2JCF 37 Hz), 166.26; C26H30F3NO5 (493.5): calcd C 63.28, H 6.13; found C
62.75, H 6.27.
(3S,1'S,2'S)-1-Ethoxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-pro-
poxy)-hex-5-ene (8 f): Reaction of ketone 7 f (232 mg, 2.00 mmol) with ent-
2 (319 mg, 1.00 mmol) according to general procedure 1 for 4 d gave the
homoallylic ether 8 f (248 mg, 0.64 mmol, 64%) as colorless needles. M.p.
(3R)-2,3-Dimethylhex-5-en-3-ol (5 f): Reaction of 4 f (179 mg, 0.50 mmol)
with sodium (29 mg, 1.25 mmol) according to general procedure 2 gave 5 f
(54 mg, 0.42 mmol, 85%). [a]2D0 14.28 (c 1, CHCl3); 1H NMR
(200 MHz, CDCl3): d 0.90 (d, J 7.0 Hz, 3H), 0.94 (d, J 7.0 Hz, 3H),
1.08 (s, 3H), 1.40 (brs, 1H), 1.69 (sept, J 7.0 Hz, 1H), 2.23 (d, J 7.0 Hz,
2H), 5.07 ± 5.22 (m, 2H), 5.78 ± 5.99 (m, 1H); 13C NMR (50 MHz, CDCl3):
d 16.90, 17.53, 22.83, 36.84, 44.12, 74.25, 118.60, 134.09; IR (film): nÄ
3380 cm 1, 3314, 3082, 2976, 2936, 2882, 1448, 1418, 1380, 1276, 1192, 1088,
1052, 912, 882; MS (70 eV, EI): m/z (%) 87 (84), 69 (34), 43 (100); C8H16O
(128.2): calcd C 74.94, H 12.58; found C 75.12, H 12.52.
608C; [a]2D0
15.08 (c 1, CHCl3); 1H NMR (200 MHz, CDCl3): d 1.03
(s, 3H), 1.16 (t, J 7.0 Hz, 3H), 1.18 (d, J 7.0 Hz, 3H), 1.74 (td, J 7.0,
4.0 Hz, 2H), 2.32 (d, J 7.0 Hz, 2H), 3.40 (qd, J 5.0, 1.0 Hz, 2H), 3.40 ±
3.58 (m, 2H), 4.01 ± 4.15 (m, 1H), 4.59 (d, J 4.0 Hz, 1H), 5.10 (dd, J 10,
2.0 Hz, 2H), 5.70 ± 5.95 (m, 1H), 6.53 (brd, J 7.5 Hz, 1H), 7.19 ± 7.43 (m,
5H); 13C NMR (50 MHz, CDCl3): d 15.05, 16.81, 23.92, 39.04, 44.02, 51.81,
1
66.11, 66.40, 74.46, 78.10, 115.79 (q, JCF 286 Hz), 118.11, 126.63, 127.80,
(3S,1'S,2'S)-1-O-Acetyl-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-
propoxy)-hex-5-en-1-ol (8a): Reaction of ketone 7a (260 mg, 2.00 mmol)
with ent-2 (319 mg, 1.00 mmol) according to general procedure 1 for 4 h
gave the homoallylic ether 8a (172 mg, 0.43 mmol, 43%) as colorless
2
1
128.15, 133.87, 141.32, 156.84 (q, JCF 35 Hz); IR (KBr): nÄ 3308 cm
,
3110, 3086, 3028, 2976, 2936, 2874, 1722, 1700, 1566, 1382, 1210, 1182, 1168,
1118, 1106, 1054, 916, 760, 724, 704; MS (70 eV, FD): m/z (%) 388 (1), 346
(1), 230 (100), 141 (23), 117 (23), 59 (15), 55 (41); C20H28F3NO3 (387.5):
calcd C 62.00, H 7.28; found C 62.19, H 7.51.
needles. M.p. 938C; [a]D20
17.88 (c 1, CHCl3); 1H NMR (200 MHz,
CDCl3): d 1.02 (s, 3H), 1.18 (d, J 7.0 Hz, 3H), 1.76 (dd, J 7.5, 7.5 Hz,
1H), 1.79 (dd, J 7.5, 7.5 Hz, 1H), 2.00 (s, 3H), 2.35 (d, J 7.5 Hz, 2H),
4.00 ± 4.25 (m, 3H), 4.61 (d, J 4.5 Hz, 1H), 5.12 (d, J 15.5 Hz, 1H), 5.13
(d, J 12.0 Hz, 1H), 5.82 (ddd, J 16, 12, 7.5 Hz, 1H), 6.41 (brd, J
8.0 Hz, 1H), 7.19 ± 7.39 (m, 5H); 13C NMR (50 MHz, CDCl3): d 16.54,
20.98, 23.81, 37.92, 43.83, 51.57, 60.65, 74.33, 77.82, 115.65 (q, 1JCF 288 Hz),
1-p-Methoxyphenoxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-pro-
poxy)-hex-5-ene (8g): Reaction of ketone 7g (388 mg, 2.00 mmol) with ent-
2 (319 mg, 1.00 mmol) according to general procedure 1 for 3 d gave the
homoallylic ether 8g (210 mg, 0.45 mmol, 45%) as colorless oil. [a]D20
1
29.38 (c 1, CHCl3); H NMR (200 MHz, CDCl3): d 1.08 (s, 3H), 1.17
(d, J 7.0 Hz, 3H), 1.78 ± 2.04 (m, 2H), 2.40 (d, J 7.0 Hz, 2H), 3.76 (s,
3H), 3.82 ± 4.06 (m, 2H), 4.04 ± 4.19 (m, 1H), 4.62 (d, J 4.5 Hz, 1H), 5.13
(d, J 12 Hz, 1H), 5.15 (d, J 16 Hz, 1H), 5.87 (ddd, J 16, 12, 7.0 Hz,
2
118.64, 126.64, 127.92, 128.36, 133.46, 140.75, 156.46 (q, JCF 37 Hz),
171.03; IR (KBr): nÄ 3412 cm 1, 3330, 3094, 3034, 2976, 2938, 2926, 1714,
1558, 1454, 1376, 1266, 1212, 1178, 1158, 1046, 916, 758, 724, 702; MS (70 eV,
EI): m/z (%) 400 (1), 386 (1), 360 (13), 71 (18), 43 (100); C20H26F3NO4
(401.4): calcd C 59.84, H 6.53; found C 59.93, H 6.82.
1H), 6.41 (brd, J 8.0 Hz, 1H), 6.66 ± 6.87 (m, 4H), 7.19 ± 7.37 (m, 5H); 13
C
NMR (50 MHz, CDCl3): d 16.63, 23.96, 38.70, 44.10, 51.67, 55.70, 64.53,
74.41, 78.16, 114.59, 115.30, 115.93 (q, 1JCF 288 Hz), 118.46, 126.67, 127.91,
(3S,1'S,2'S)-O-Pivaloyl-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-pr-
opoxy)-hex-5-en-1-ol (8b): Reaction of ketone 7b (344 mg, 2.00 mmol)
with ent-2 (319 mg, 1.00 mmol) according to general procedure 1 for 4 d
gave the homoallylic ether 8b (111 mg, 0.25 mmol, 25%) as colorless oil.
2
128.33, 133.77, 140.89, 152.83, 153.73, 156.41 (q, JCF 37 Hz); IR (film):
nÄ 3316 cm 1, 3074, 2976, 2938, 1712, 1510, 1456, 1230, 1212, 1180, 1042,
826, 704; MS (70 eV, FD): m/z (%) 465 (38), 352 (52), 230 (100), 124 (57),
107 (49), 95 (27); C25H30F3NO4 (465.5): calcd C 64.50, H 6.50; found C
[a]2D0
16.88 (c 1, CHCl3); 1H NMR (200 MHz, CDCl3): d 1.15 (s,
65.05, H 6.82; HRMS (M ): calcd 465.2127; found 465.2126.
9H), 1.17 (d, J 7.5 Hz, 3H), 1.43 (s, 3H), 1.62 ± 1.91 (m, 2H), 2.35 (d, J
7.5 Hz, 2H), 3.99 ± 4.25 (m, 3H), 4.62 (d, J 3.5 Hz, 1H), 5.12 (d, J 12 Hz,
1H), 5.13 (d, J 16 Hz, 1H), 5.83 (ddd, J 16, 12, 7.5 Hz, 1H), 6.41 (brd,
(3S,1'S,2'S)-1-Allyloxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-pro-
poxy)-hex-5-ene (8h): Reaction of ketone 7h (256 mg, 2.00 mmol) with ent-
1868
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Chem. Eur. J. 1998, 4, No. 9