5
856 J . Org. Chem., Vol. 65, No. 18, 2000
Notes
Sch em e 3
124.12, 126.99, 131.20; EI-MS m/z 151 (100), 150, 77. Anal. Calcd
for C
9
H
10
N
2
O
5
: C, 47.79; H, 4.46; N, 12.38. Found: C, 47.85; H,
4
1
3
(
1
.40; N, 12.02. Syn d ia ster eom er : IR (Nujol) 3477, 1605, 1548,
-
1
1
519, 1389, 1345 cm ; H NMR (CDCl
H), 2.9 (bs, 1H), 4.26-4.34 (m, 1H), 5.2 (d, J ) 8.8 Hz, 1H), 7.6
) δ 16.24, 74.91, 87.73,
23.62, 123.96, 127.88, 131.20; EI-MS m/z 151 (100), 150, 77.
: C, 47.79; H, 4.46; N, 12.38. Found:
C, 47.85; H, 4.40; N, 12.02.
-Nitr o-1-p h en ylp en ta n -3-ol (2d ). An ti d ia ster eom er : IR
3
) δ 1.4 (d, J ) 6.9 Hz,
d, 2H), 8.4 (d, 2H); 13C NMR (CDCl
3
9 10 2 5
Anal. Calcd for C H N O
4
-
1 1
(neat) 3435, 1602, 1546, 1360 cm ; H NMR (CDCl
3
) δ 1.55 (d,
J ) 6.76 Hz, 3H), 1.7-1.95 (m, 2H), 2.3 (bs, 1H), 2.64-3.0 (m,
2
H), 3.85-3.96 (ddd, J ) 3.7, 6.96 and 8.99 Hz, 1H), 4.44-4.63
13
(
(
1
5
dq, J ) 6.79 and 6.79 Hz, 1H), 7.18-7.4 (m, 5H); C NMR
CDCl ) δ 16.24, 31.44, 34.69, 71.95, 87.77, 126.28, 128.45,
28.63, 40.86; EI-MS m/z 162 (M - HNO ), 145, 105, 91 (100),
7. Anal. Calcd for C11 C, 63.14; H, 7.23; N, 6.69.
3
2
H
3
15NO :
Found: C, 63.85; H, 7.40; N, 6.52. Syn d ia ster eom er : IR (neat)
-
1
1
3
6
4
6
1
3
435, 1602, 1546, 1360 cm ; H NMR (CDCl ) δ 1.56 (d, J )
.88 Hz, 3H), 1.7-1.95 (m, 2H), 2.3 (bs, 1H), 2.64-3.0 (m, 2H),
.15-4.24 (dt, J ) 3.5 and 9.24 Hz, 1H), 4.44-4.63 (dq, J )
.79 and 6.79 Hz, 1H), 7.18-7.4 (m, 5H); 13C NMR (CDCl
) δ
3
2.51, 31.92, 34.56, 71.03, 86.39, 126.28, 128.45, 128.63, 140.86;
), 145, 105, 91 (100), 57. Anal. Calcd
: C, 63.14; H, 7.23; N, 6.69. Found: C, 63.85; H,
EI-MS m/z 162 (M - HNO
for C11
.40; N, 6.52.
-Meth yl-4-n itr otr id eca n -5-ol (2e). An ti d ia ster eom er :
2
H
15NO
3
7
2
-
1
1
IR (neat) 3434, 1549 cm
3
2
;
H NMR (CDCl
3
) δ 0.92-0.95 (m,
H), 0.95-1.0 (m, 6H), 1.2-1.38 (m, 10H), 1.4-1.61 (m, 4H),
1
3
.0-2.4 (m, 3H), 3.94-4.02 (m, 1H), 4.51-4.58 (m, 1H); C NMR
) δ 14.09, 21.19, 22.64, 23.16, 25.8, 25.62, 29.18, 29.36,
1.80, 33.06, 36.60, 39.32, 72.52, 90.45; EI-MS m/z 213 (M -
NO : C,
(CDCl
3
Exp er im en ta l Section
3
To a cold solution (-78 °C) of R-nitro ketone 1 (1.0 mmol) in
NO ), 169, 141, 99, 57, 43 (100). Anal. Calcd for C
H
14 29
2
3
1
0 mL of dry CH
2
Cl
2
was added TiCl
4
(1.5 mmol) to give
64.83; H, 11.27; N, 5.4. Found: C, 63.95; H, 11.30; N, 5.32. Syn
-
1 1
immediately a clear yellow solution, which was stirred for 15
min at this temperature. The complex BH ‚SMe (1.5 mmol) in
mL of CH Cl was then added. After 15 min, 25 mL of 1 N
d ia ster eom er : IR (neat) 3434, 1549 cm ; H NMR (CDCl ) δ
3
0.92-0.95 (m, 3H), 0.95-1.0 (m, 6H), 1.2-1.38 (m, 10H), 1.4-
1.61 (m, 4H), 2.0-2.4 (m, 3H), 3.78-3.83 (m, 1H), 4.48-4.51 (m,
3
2
5
2
2
1H); 13C NMR (CDCl ) δ 14.09, 21.31, 22.64, 23.01, 25.26, 25.62,
HCl was added, and the reaction was warmed to room temper-
ature. The organic layer was separated, the aqueous layer was
3
29.30, 29.40, 31.80, 33.65, 36.60, 39.32, 72.37, 91.14; EI-MS m/z
washed with CH
trated in vacuo. The resulting residue was partitioned between
Et O and H O. The etheral layer was washed with water and
brine, dried over Na SO , and concentrated in vacuo. The crude
2
Cl
2
, and the combined organics were concen-
213 (M - NO ), 169, 141, 99, 57, 43 (100). Anal. Calcd for C14H29-
2
NO : C, 64.83; H, 11.27; N, 5.4. Found: C, 63.95; H, 11.30; N,
3
2
2
5.32.
2
4
6-Nitr oocta d eca n -7-ol (2f). An ti d ia ster eom er : IR (neat)
-
1
1
nitro alcohol 2, obtained as a diastereomeric mixture of syn and
anti product, was purified, if necessary, by flash cromatography
3435, 1550, 1378 cm ; H NMR (CDCl ) δ 0.83-0.9 (m, 6H),
3
1.2-1.35 (m, 24H), 1.4-1.58 (m, 3H), 1.68-1.72 (m, 1H), 1.98-
1
3
(
EtOAc/hexane ) 2:8). The syn/ anti ratios were determined by
NMR spectroscopy.
-Nitr o-1-p h en ylh ep ta n -1-ol (2a ). An ti d ia ster eom er : IR
2.18 (m, 1H), 3.95-4.02 (m, 1H), 4.38-4.47 (m, 1H); C NMR
(CDCl ) δ 13.89, 14.12, 22.30, 22.68, 25.28, 25.36, 25.64, 27.88,
3
2
29.09, 29.30, 29.32, 29.45, 29.60, 31.08, 31.15, 33.18, 72.38, 92.35;
-
1
1
(
neat) 3614, 3570, 1605, 1551, 1379 cm ; H NMR (CDCl
3
) δ
.74-0.93 (m, 3H), 1.1-1.4 (m, 6H), 1.72-1.91 (m, 1H), 2.01-
.3 (m, 1H), 2.75 (bs, 1H), 4.6-4.72 (ddd, J ) 3.17, 4.84 and
0.86 Hz, 1H), 5.18 (d, J ) 4.8 Hz, 1H), 7.3-7.42 (m, 5H); 13
) δ 14.35, 22.74, 25.99, 28.17, 31.52, 74.74, 93.72,
26.65, 129.19, 129.25, 138.95; EI-MS m/z 190 (M - HNO ), 133,
07 (100), 105, 77. Anal. Calcd for C13 : C, 65.8; H, 8.07;
EI-MS m/z 269 (M - NO
Calcd for C18 : C, 68.53; H, 11.82; N, 4.44. Found: C,
68.75; H, 11.30; N, 4.46. Syn d ia ster eom er : IR (neat) 3435,
2
), 183, 140, 113, 70, 55 (100). Anal.
0
2
1
H37NO
3
-1
1
C
1550, 1378 cm
3
; H NMR (CDCl ) δ 0.83-0.9 (m, 6H), 1.2-
NMR (CDCl
3
1.35 (m, 24H), 1.4-1.58 (m, 3H), 1.68-1.72 (m, 1H), 1.98-2.18
(m, 1H), 3.8-3.88 (m, 1H), 4.38-4.47 (m, 1H); 13C NMR (CDCl
)
3
1
1
2
H
19NO
3
δ 13.89, 14.12, 22.30, 22.68, 25.28, 25.36, 25.64, 27.88, 29.09,
N, 5.9. Found: C, 65.4; H, 8.02; N, 6.02.
29.30, 29.32, 29.45, 29.52, 30.45, 31.90, 33.62, 72.06, 92.88; EI-
2
-Meth yl-3-n itr oocta n -4-ol (2b). An ti d ia ster eom er : IR
MS m/z 269 (M - NO
for C18 : C, 68.53; H, 11.82; N, 4.44. Found: C, 68.75; H,
11.30; N, 4.46.
2-Nitr o-1-p h en ylp en ta n -3-ol (2g). An ti d ia ster eom er : IR
2
), 183, 140, 113, 70, 55 (100). Anal. Calcd
-
1
1
(
7
2
neat) 3436, 1547, 1375 cm ; H NMR (CDCl
3
) δ 0.89 (t, J )
.2 Hz, 3H), 0.97-1.18 (m, 6H), 1.20-1.58 (m, 6H), 1.98 (s, 1H),
.33-2.45 (m, 1H), 4.0-4.08 (m, 1H), 4.33 (dd, J ) 5.9 and 6.9
H37NO
3
1
3
-1
1
Hz, 1H); C NMR (CDCl
3
) δ 13.93, 18.35, 19.56, 22.41, 27.86,
8.36, 32.39, 70.44, 97.40; EI-MS m/z 142 (M - HNO ), 127, 100,
5, 69, 57, 56 (100). Anal. Calcd for C : C, 57.12; H,
0.12; N, 7.40. Found: C, 56.84; H, 10.26; N, 7.12. Syn
3
(neat) 3435, 1605, 1548, 1376 cm ; H NMR (CDCl ) δ 1.0 (t,
2
8
1
2
J ) 7.35 Hz, 3H), 1.45-1.62 (m, 2H), 3.15-3.35 (m, 2H), 3.9-
3.98 (ddd, J ) 5.17, 5.17 and 10.38 Hz, 1H), 4.0 (bs, 1H), 4.6-
9 3
H19NO
4.72 (m, 1H), 7.1-7.32 (m, 5H); 13C NMR (CDCl
) δ 10.00, 26.48,
3
-
1
1
d ia ster eom er : IR (neat) 3436, 1547, 1375 cm
;
H NMR
34.60, 73.43, 93.63, 127.16, 128.74, 128.81, 136.2; EI-MS m/z
162 (M - HNO ), 145, 133, 105, 91 (100), 77, 57. Anal. Calcd for
: C, 63.14; H, 7.23; N, 6.69. Found: C, 63.35; H, 7.30;
N, 6.56. Syn d ia ster eom er : IR (neat) 3435, 1605, 1548, 1376
(
CDCl
3
) δ 0.89 (t, J ) 7.2 Hz, 3H), 0.97-1.18 (m, 6H), 1.20-
.58 (m, 6H), 1.98 (s, 1H), 2.33-2.45 (m, 1H), 4.0-4.08 (m, 1H),
.17 (dd, J ) 4.15 and 9.12 Hz, 1H); 13C NMR (CDCl
) δ 13.93,
8.80, 18.97, 22.41, 27.85, 28.38, 32.45, 69.52, 98.2; EI-MS m/z
60, 143, 127, 100, 85, 69, 57, 56 (100). Anal. Calcd for C
: C, 57.12; H, 10.12; N, 7.40. Found: C, 56.84; H, 10.26; N,
.12.
-Nitr o-1-(4-n itr op h en yl)p r op a n -1-ol (2c). An ti d ia ste-
2
1
4
1
1
11 3
C H15NO
3
-
1 1
cm ; H NMR (CDCl
3
) δ 1.0 (t, J ) 7.35 Hz, 3H), 1.45-1.62 (m,
9
19
H -
2H), 3.15-3.35 (m, 2H), 3.75-3.86 (ddd, J ) 4.11, 5.94 and 10.25
1
3
NO
3
Hz, 1H), 4.0 (bs, 1H), 4.6-4.72 (m, 1H), 7.1-7.32 (m, 5H);
NMR (CDCl ) δ 9.74, 26.62, 36.37, 72.67, 93.68, 127.37, 128.74,
128.81, 135.4; EI-MS m/z 162 (M - HNO ), 145, 133, 105, 91
(100), 77, 57. Anal. Calcd for C11 : C, 63.14; H, 7.23; N,
6.69. Found: C, 63.35; H, 7.30; N, 6.56.
2-Meth yl-4-n itr oh ep ta n -3-ol (2h ). An ti d ia ster eom er : IR
C
7
3
2
2
-
1
r eom er : IR (Nujol) 3477, 1605, 1548, 1519, 1389, 1345 cm
H NMR (CDCl
.8 (dq, J ) 3.2 and 6.9 Hz, 1H), 5.56 (d, J ) 3.2 Hz, 1H), 7.6 (d,
H), 8.4 (d, 2H); C NMR (CDCl
;
H15NO
3
1
3
) δ 1.5 (d, J ) 6.9 Hz, 3H), 2.9 (bs, 1H), 4.64-
4
2
1
3
-1
1
3
) δ 11.86, 72.73, 86.78, 123.62,
3
(neat) 3468, 1551, 1377 cm ; H NMR (CDCl ) δ 0.94 (t, J )