Capriati et al.
µm film thickness) capillary column, Det. FID 300 °C, column
59 (13), 43 (13); FT-IR (film, cm-1) 3452, 2972, 1451, 1367,
1190, 958, 754, 704.
(2S,3R)-(+)-2,3-Epoxy-1,2-diph en ylbu tan -1-on e (3h ): col-
orless oil (bp 47 °C, 10-3 Torr); 70% yield, convn >98%, dr >98:
2, er >99:1 [tRmajor ) 39.69 min, tRminor ) 40.47 min on a
Chiraldex B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25 µm film
thickness) capillary column, Det. FID 300 °C, column head
head pressure 12 psi, He flow 1.5 mL/min, split ratio 100/1,
oven temperature 100 °C]; [R]20 ) -38.0 (c 1, CHCl3).
D
(2S,3S)-(-)-2-P h en yl-2,3-ep oxybu ta n e (3b): colorless oil
(bp 47 °C, 10-3 Torr); 51% yield; convn > 98%, dr >98:2, er
>99:1 [tRmajor ) 4.22 min, tRminor ) 4.32 min on a Chiraldex
B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25 µm film thickness)
capillary column, Det. FID 300 °C, column head pressure 12
pressure 12 psi, He flow 1.5 mL/min, split ratio 100/1, oven
1
temperature 150 °C]; [R]20 ) +198.7 (c 1, CHCl3); H NMR
psi, He flow 1.5 mL/min, split ratio 100/1, oven temperature
D
1
100 °C]; [R]20 ) -16.0 (c 1, CHCl3); H and 13C NMR have
(500 MHz) δ 1.13 (d, J ) 5.5 Hz, 3 H), 3.57 (q, J ) 5.5 Hz, 1
H), 7.24-7.56 (m, 8 H), 8.03 (d, J ) 7.5 Hz, 2 H); 13C NMR
(125 MHz) δ 13.4, 59.2, 68.6, 126.8, 128.3, 129.7, 129.8, 130.0,
133.2, 133.5, 134.2, 195.6; GC-MS (70 eV) m/z 238 (63, M+),
223 (7), 165 (55), 194 (2), 165 (55), 133 (20), 105 (100), 77 (57),
51 (15); FT-IR (film, cm-1) 3340, 3029, 2969, 1682, 1598, 1494,
1448, 1276, 1210, 971, 832, 700.
D
been reported in the case of (2R*,3R*)-3b in ref 20; GC-MS
(70 eV) m/z 148 (49, M+), 147 (16), 133 (100), 119 (46), 104
(73), 103 (94), 91 (35), 78 (81), 65 (15); FT-IR (film, cm-1) 3059,
1448, 1383, 1277, 1071, 1028, 842, 775, 742, 700.
(4S,5S)-(+)-4-P h en yl-4,5-ep oxy-1-h exen e (3c): colorless
oil (bp 43 °C, 10-3 Torr); 74% yield; convn 98%, dr >98:2, er
97:3 [tRmajor ) 9.70 min, tRminor ) 10.04 min on a Chiraldex
B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25 µm film thickness)
capillary column, Det. FID 300 °C, column head pressure 12
psi, He flow 1.5 mL/min, split ratio 100/1, oven temperature
100 °C]; [R]20D ) +6.6 (c 1, CHCl3); 1H and 13C NMR have been
reported in the case of (4R*,5R*)-3c in ref 21; GC-MS (70 eV)
m/z 174 (3, M+), 173 (11), 159 (11), 145 (17), 129 (67), 120 (30),
(1S,2R,3S)-1-P h en yl-2,3-ep oxybu ta n -1-ol (3i): colorless
oil; 52% yield; convn 67%, er 98:2 ascertained by 1H NMR (500
MHz, CCl4 with CDCl3 as external standard) in the presence
of the chiral solvating agent (CSA) (R)-(-)-1-phenyl-2,2,2-
trifluoroethanol (CSA/epoxide molar ratio ) 3/1) δ 1.84 (dmajor
,
J ) 6.0 Hz, 3 H, CHCH3), 1.85 (dminor, J ) 6.0 Hz, 3 H, CHCH3);
1
[R]20 ) +69.4 (c 1, CHCl3); H NMR (500 MHz) δ: 1.72 (d, J
D
115 (48), 105 (100), 91 (16), 77 (36), 51 (12); FT-IR (film, cm-1
3063, 1642, 1449, 1264, 990, 916, 748, 700.
)
) 6.0 Hz, 3 H), 2.35 (d, J ) 4.0 Hz, 1 H, exchanges with D2O),
3.24 (q, J ) 6.0 Hz, 1 H), 5.01 (d, J ) 4.0 Hz, 1 H), 6.99-7.36
(m, 10 H); 13C NMR (125 MHz) δ: 14.9, 61.8, 68.2, 74.3, 126.1,
127.3, 127.5, 127.6, 128.1, 128.3, 136.7, 139.8; GC-MS (70 eV)
m/z 222 [M+-H2O] (3), 196 (55), 167 (26), 152 (15), 134 (62),
133 (54), 105 (100), 91 (18), 77 (53), 51 (14), 43 (6); FT-IR (film,
cm-1) 3445, 3031, 1496, 1448, 1027, 756, 712.
(1R,2R,3S)-1-P h en yl-2,3-ep oxybu ta n -1-ol (3j): colorless
oil; 52% yield; convn 67%, er 98:2 ascertained by 1H NMR (500
MHz, CCl4 with CDCl3 as external standard) in the presence
of the chiral solvating agent (CSA) (R)-(-)-1-phenyl-2,2,2-
(3S,4S)-(+)-2-Meth yl-3-ph en yl-3,4-epoxypen tan -2-ol (3d):
colorless oil (bp 47 °C, 10-3 Torr); 51% yield; convn 83%, dr
>98:2, er >99:1 [tRmajor ) 6.29 min, tRminor ) 6.13 min on a
Chiraldex B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25 µm film
thickness) capillary column, Det. FID 300 °C, column head
pressure 12 psi, He flow 1.5 mL/min, split ratio 100/1, oven
temperature 100 °C]; [R]20D ) +7.0 (c 1, CHCl3); 1H NMR (300
MHz) δ: 1.06 (s, 3 H), 1.43 (s, 3 H), 1.73 (d, J ) 5.9 Hz, 3 H),
2.49 (s, 1 H, exchanges with D2O), 3.05 (q, J ) 5.9 Hz, 3 H),
7.24-7.37 (m, 5 H); 13C NMR (75 MHz) δ 12.7, 23.9, 28.6, 60.6,
68.5, 69.1, 125.8, 126.2, 126.5, 133.2; GC-MS (70 eV) m/z 174
(3, M+), 173 (11), 159 (11), 145 (17), 129 (67), 120 (30), 115
(48), 105 (100), 91 (16), 77 (36), 51 (12); FT-IR (film, cm-1) 3063,
1642, 1449, 1264, 990, 916, 748, 700.
trifluoroethanol (CSA/epoxide molar ratio ) 3/1) δ 1.81 (dmajor
,
J ) 5.5 Hz, 3 H, CHCH3), 1.82 (dminor, J ) 5.5 Hz, 3 H, CHCH3);
[R]20 ) -44.6 (c 1, CHCl3); 1H NMR (500 MHz) δ 1.69 (d, J )
D
6.0 Hz, 3 H), 2.32 (d, J ) 3.0 Hz, 1 H, exchanges with D2O),
3.20 (q, J ) 6.0 Hz, 1 H), 4.99 (d, J ) 3.0 Hz, 1 H), 7.11-7.24
(m, 10 H); 13C NMR (125 MHz) δ 13.9, 61.1, 66.4, 74.4, 126.5,
127.4, 127.5, 127.7, 127.8, 137.8, 139.9; GC-MS (70 eV) m/z
222 [M+ - H2O] (2), 196 (61), 167 (30), 165 (31), 152 (18), 134
(69), 133 (60), 105 (100), 91 (15), 77(53), 51 (13), 43 (3); FT-IR
(film, cm-1) 3445, 3032, 1495, 1447, 1059, 756, 711.
(1S,2R)-(+)-1-Deu ter o-1-p h en yl-1,2-ep oxyp r op a n e (3e):
colorless oil (bp 47 °C, 10-3 Torr); >98% yield, convn > 98%,
>98% D, dr >98:2, er >99:1 [tRminor ) 8.37 min, tRmajor ) 9.12
min on a Chiraldex B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25
µm film thickness) capillary column, Det. FID 300 °C, column
head pressure 12 psi, He flow 1.5 mL/min, split ratio 100/1,
(1S,2R,3R)-1-P h en yl-2,3-ep oxybu ta n -1-ol (3k ): white
solid; mp 147-148 °C (hexane); 85% yield; convn >98%, er
98:2 ascertained by 1H NMR (500 MHz, CCl4 with CDCl3 as
external standard) in the presence of the chiral solvating agent
(CSA) (R)-(-)-1-phenyl-2,2,2-trifluoroethanol (CSA/epoxide mo-
lar ratio ) 3/1) δ 1.14 (dminor, J ) 5.5 Hz, 3 H, CHCH3), 1.15
oven temperature 100 °C]; [R]20 ) +38.0 (c 1, CHCl3).
D
(2S,3R)-(+)-2-P h en yl-2,3-ep oxybu ta n e (3f): colorless oil
(bp 47 °C, 10-3 Torr); 84% yield; convn > 98%, dr >98:2, er
1
>99:1 ascertained by H NMR (500 MHz, CCl4 with CDCl3 as
(dminor, J ) 5.5 Hz, 3 H, CHCH3); [R]20 ) +20.6 (c 1, CHCl3);
external standard) in the presence of the chiral solvating agent
D
1H NMR (500 MHz) δ 0.99 (d, J ) 5.5 Hz, 3 H), 3.67 (q, J )
5.5 Hz, 1 H), 4.93 (s, 1 H), 7.01-7.28 (m, 10 H); 13C NMR (125
MHz) δ 14.7, 57.2, 68.5, 76.0, 126.9, 127.4, 127.7, 127.8, 127.9,
128.1, 135.0, 140.1; GC-MS (70 eV) m/z 222 [M+ - H2O] (4),
196 (22), 165 (16), 134 (70), 133 (64), 105 (100), 91 (13), 77
(51), 51 (12); FT-IR (KBr, cm-1) 3467, 2927, 1447, 1134, 1069,
758, 709. Anal. Calcd for C16H16O2: C, 79.97; H, 6.71. Found:
C, 80.22; H, 6.70.
(CSA) (R)-(-)-1-phenyl-2,2,2-trifluoroethanol (CSA/epoxide mo-
lar ratio ) 3/1) δ 1.74 (sminor, 3 H, CCH3Ph), 1.75 (smajor, 3 H,
1
CCH3Ph); [R]20 ) +26.7 (c 1, CHCl3); H NMR (300 MHz) δ
D
0.98 (d, J ) 5.5 Hz, 3 H), 1.64 (s, 3H), 3.17 (q, J ) 5.5 Hz, 1
H), 7.24-7.34 (m, 5H); 13C NMR (125 MHz) δ 14.4, 24.5, 61.2,
62.6, 126.5, 127.0, 128.0, 138.6; GC-MS (70 eV) m/z 148 (26,
M+), 147 (100), 133 (6), 104 (75), 91 (7), 78 (52), 77 (33), 63
(5), 51 (14), 43 (10); FT-IR (film, cm-1) 3030, 2967, 1605, 1445,
1376, 1259, 765, 702.
(1R,2R,3R)-1-P h en yl-2,3-epoxybu tan -1-ol (3l): white solid;
mp 95-96 °C (hexane); 85% yield; convn >98%, er 98:2
ascertained by 1H NMR (500 MHz, CCl4 with CDCl3 as
external standard) in the presence of the chiral solvating agent
(CSA) (R)-(-)-1-phenyl-2,2,2-trifluoroethanol (CSA/epoxide mo-
lar ratio ) 3/1) δ 1.17 (dminor, J ) 5.5 Hz, 3 H, CHCH3), 1.18
(3S,4R)-(+)-2-Meth yl-3-ph en yl-3,4-epoxypen tan -2-ol (3g):
colorless oil (bp 47 °C, 10-3 Torr); 60% yield; convn 80%, dr
>98:2, er 99:1 [tRminor ) 31.48 min, tRmajor ) 33.59 min on a
Chiraldex B-DM (Astec) (30 m × 0.25 mm i.d. × 0.25 µm film
thickness) capillary column, Det. FID 300 °C, column head
pressure 12 psi, He flow 1.5 mL/min, split ratio 100/1, oven
temperature 100 °C]; [R]20D ) +35.4 (c 1, CHCl3); 1H NMR (500
MHz) δ 0.96 (d, J ) 5.5 Hz, 3 H), 1.10 (s, 3 H), 1.32 (s, 3 H),
2.20 (s, 1 H, exchanges with D2O), 3.60 (q, J ) 5.5 Hz, 1 H),
7.24-7.31 (m, 5 H); 13C NMR (125 MHz) δ: 15.3, 25.4, 26.9,
(dmajor, J ) 5.5 Hz, 3 H, CHCH3); [R]20 ) +53.7 (c 1, CHCl3);
D
1H NMR (500 MHz) δ 1.03 (d, J ) 5.5 Hz, 3 H), 3.62 (q, J )
5.5 Hz, 1 H), 4.85 (s, 1 H), 6.96-7.28 (m, 10 H); 13C NMR (125
MHz) δ 14.8, 56.4, 68.5, 76.1, 127.6, 127.7, 128.0, 128.1, 128.3,
135.0, 139.0; GC-MS (70 eV) m/z 222 [M+ - H2O] (4), 196
(19), 178 (9), 167 (48), 134 (100), 133 (90), 105 (97), 91 (14), 77
(57), 51 (14), 43 (5); FT-IR (KBr, cm-1) 3415, 1456, 995, 926,
55.9, 70.4, 70.8, 127.6, 135.9; GC-MS (70 eV) m/z 148 [M+
-
44] (19), 134 (65), 133 (100), 115 (13), 105 (69), 91 (15), 77 (29),
3334 J . Org. Chem., Vol. 69, No. 10, 2004