4
66
K. Okamoto et al. / Tetrahedron: Asymmetry 12 (2001) 463–467
(
CDCl , 67.8 MHz) l: 8.8, 16.5, 19.1, 28.5, 56.0, 57.8,
8.5, 65.8, 78.5, 82.6, 85.4, 125.8, 126.1, 126.4, 126.8,
4.2.5. (2S,1%S)-N-(1-Ethyl-2,4-hexadienyl)-2-amino-1,1-
diphenyl-3-propanol 6. To a solution of 5c (100 mg, 0.21
mmol) in methanol (7 mL) was added 30% aqueous
H O (3 ml) and 3N aqueous NaOH (1 mL) at 0°C,
and then the resulting mixture was stirred at 0°C for 1
h and at room temperature for 45 min. After NaHSO3
was added to the mixture, methanol was removed
under reduced pressure and the residue was extracted
with AcOEt. The combined extracts were washed with
3
5
1
2
27.9, 128.2, 144.8, 146.6; IR (CHCl ) 3341, 3039, 2969,
3
−
1
040, 1968, 1454, 1375 cm ; MS FAB: (m/z) 476
2
2
+
(MH , 67), 391 (71), 249 (100), 193 (58); HR-MS
+
(
FAB+) calcd for C H FeNO (MH ): 476.1524.
2
6
30
4
Found: 476.1530.
4
4
.2.2. (1%S,2%S)-N-Tricarbonyliron[(h -2-5)-1-ethyl-2,4-
hexadienyl]-2-amino-1,1-diphenylethanol 5a. Compound
a was prepared by the same procedure described
a saturated NaHCO solution and a saturated NaCl
3
5
solution, dried with Na SO , and concentrated in
2
4
2
8
1
above: [h]D +12.17 (c 0.641, CHCl ); H NMR (CDCl ,
vacuo. The residue was purified by flash column chro-
3
3
2
3
1
70 MHz) l: 0.76 (dd, 1H, J=8.9, 8.1 Hz), 0.89 (dd,
H, J=7.3, 7.0 Hz), 1.18 (qd, 1H, J=5.9, 7.6 Hz),
.29–1.45 (m, 2H), 1.39 (d, 3H, J=5.9 Hz), 1.60–1.82
matography (hexane/ethyl acetate=40/1) to give 6 (39.9
2
1
1
mg, 57%): [h]D −58.02 (c 0.329, CHCl3); H NMR
(CDCl , 270 MHz) l: 0.67 (dd, 3H, J=7.3, 7.6 Hz),
3
(
m, 1H), 2.19 (ddd, 1H, J=8.9, 3.0 Hz), 3.07 (d, 1H,
0.95 (d, 3H, J=6.5 Hz), 1.11–1.39 (m, 4H), 1.76 (d, 3H,
J=6.8 Hz), 2.36–2.44 (m, 1H), 3.78 (q, 1H, J=6.5 Hz),
J=11.9 Hz), 3.52 (d, 1H, J=11.9 Hz), 5.01 (dd, 1H,
J=7.6, 12.4 Hz), 5.04 (dd, 1H, J=8.1, 12.4 Hz), 7.18–
5.20 (dd, 1H, J=8.1, 14.9 Hz), 5.69 (qd, 1H, J=6.8,
1
3
13
7
1
1
.50 (m, 10H); C NMR (CDCl , 67.8 MHz) l: 10.1,
13.5 Hz), 5.84–6.08 (m, 2H), 7.12–7.62 (m, 10H);
C
3
9.1, 29.9, 56.1, 58.0, 62.5, 65.5, 76.2, 82.7, 85.4, 125.9,
26.1, 126.9, 127.0, 128.2, 128.3, 145.4, 145.5; IR
NMR (CDCl , 67.8 MHz) l: 10.3, 17.8, 18.1, 28.8,
3
56.6, 60.1, 78.1, 125.9, 126.2 (×2), 126.6, 127.8, 128.0,
(CHCl ) w: 3410, 3040, 2965, 2865, 2040, 1968, 1454,
128.7, 131.0, 131.1, 134.1, 145.2, 147.3; IR (CHCl ) w:
3
3
−
1
+
−1
1
375 cm ; MS FAB: (m/z) 462 (MH , 92), 377 (100),
3335, 3061, 2965, 2928, 2865, 1454, 1374 cm ; MS
+
2
49 (82), 193 (53); HR-MS (FAB+) calcd for
FAB: (m/z) 336 (MH , 60), 210 (10), 152 (32), 109
+
+
C H FeNO (MH ): 462.1367. Found: 462.1364.
(100); HR-MS (FAB+) calcd for C H NO (MH ):
2
5
28
4
23 30
3
36.2327. Found: 336.2325.
4
4
2
.2.3. (2R,1%S,2%S)-N-Tricarbonyliron[(h -2-5)-1-ethyl-
,4-hexadienyl]-2-amino-1,1-diphenylethanol 5b. Com-
4.3. General procedure for catalytic ethylation of alde-
hydes with 5a–d and 6
pound 5b was prepared by the same procedure
3
1
1
described above: [h] +30.42 (c 0.933, CHCl3);
H
D
NMR (CDCl , 270 MHz) l: 0.59 (dd, 1H, J=8.9, 9.2
A typical procedure for enantioselective addition of
diethylzinc to aldehydes: (S)-1-phenyl-1-propanol 7A.
To a solution of 5a (40 mg, 0.087 mmol) in toluene (2
ml) was added diethylzinc (1.1 M solution in toluene,
1.19 ml, 1.3 mmol) under an argon atmosphere at 0°C
and the resulting solution was stirred at room tempera-
ture for 1 h. A solution of benzaldehyde (92.3 mg, 0.87
mmol) in toluene (0.8 ml) was added to the mixture at
0°C and the resulting mixture was stirred for 18 h.
3
Hz), 0.86 (t, 3H, J=7.3 Hz), 0.95 (d, 3H, J=6.2 Hz),
1
(
.14 (qd, 1H, J=5.9, 3.5 Hz), 1.20–1.37 (m, 2H), 1.43
d, 3H, J=5.9 Hz), 1.60–1.80 (m, 1H), 2.18 (ddd, 1H,
J=3.5, 9.2, 9.7 Hz), 3.95 (q, 1H, J=6.2 Hz), 4.20–4.50
m, 1H), 4.95 (dd, 1H, J=8.9, 4.9 Hz), 5.07 (dd, 1H,
(
13
J=3.5, 4.9 Hz), 7.10–7.60 (m, 10H); C NMR (CDCl3,
6
6
1
2
7.8 MHz) l: 10.1, 14.8, 19.1, 30.7, 54.7, 58.1, 58.3,
5.8, 79.1, 82.1, 85.4, 125.7, 126.1, 126.4, 126.9, 127.9,
28.3, 144.7, 146.2; IR (CHCl ): w 3448, 3037, 2970,
After being quenched with a saturated NH Cl solution,
3
4
−
1
041, 1968, 1452, 1373 cm ; MS FAB: (m/z) 476
the resulting mixture was extracted with AcOEt. The
+
(MH , 65), 391 (80), 249 (100), 193 (62); HR-MS
combined extracts were washed with a saturated NH Cl
4
+
+
(FAB ) calcd for C H FeNO (MH ): 476.1524.
solution and a saturated NaCl solution, dried with
26
30
4
Found: 476.1511.
MgSO , and concentrated in vacuo. The residue was
4
purified by flash column chromatography (hexane/ethyl
acetate=5/1) to give (S)-1-phenyl-1-propanol 7A (27.3
mg, 24%). The e.e. was determined to be 58% by HPLC
analysis using a DAICEL Chiralcel OD column (hex-
4
4
.2.4. (2S,1%S,2%S)-N-Tricarbonyliron[(h -2-5)-1-ethyl-2,
-hexadienyl]-2-amino-1,1-diphenyl-3-methylbutanol 5d.
4
Compound 5d was prepared by the same procedure
3
1
1
3g
described above: [h] +38.24 (c 1.037, CHCl3);
H
ane/i-PrOH 99/1, flow rate: 1 ml/min): (R)-7A 20.3
D
NMR (CDCl , 270 MHz) l: 0.57 (t, 1H, J=8.9 Hz),
min, (S)-7A 29.1 min. For 1-(4-methylphenyl)-1-
3
3m
.71 (d, 3H, J=7.0 Hz), 0.79 (dd, 3H, J=6.8, 7.6 Hz),
.84 (d, 3H, J=7.3 Hz), 1.07 (qd, 1H, J=5.9, 8.4 Hz),
.13–1.30 (m, 2H), 1.39 (d, 3H, J=5.9 Hz), 1.42–1.51
propanol 7B: AS column (hexane/i-PrOH 99/1, flow
rate: 0.5 ml/min); (R)-7B 29.8 min, (S)-7B 35.2 min.
3g
For 1-(4-methoxyphenyl)-1-propanol 7C: OD column
(hexane/i-PrOH 97.5/2.5, flow rate: 0.7 ml/min); (R)-7C
33.2 min, (S)-7C 39.6 min. For 1-(3,4-dime-
3e
thoxyphenyl)-1-propanol 7D: OD column (hexane/i-
PrOH 97.5/2.5, flow rate: 1 ml/min); (R)-7D 59.7 min,
(S)-7D 54.9 min. For 1-(4-chlorophenyl)-1-propanol
1
3
3
1
8
1
1
9.1, 22.4, 28.3, 32.2, 57.9, 59.5, 64.5, 67.5, 78.3, 81.9,
3d
4.7, 125.7, 126.07, 126.15, 126.6, 127.9 (×2), 145.4,
7E: OD column (hexane/i-PrOH 99/1, flow rate: 1
ml/min); (R)-7E 13.1 min, (S)-7E 14.0 min. For 1-
48.9; IR (CHCl ) w: 3348, 3060, 2963, 2039, 1968,
3
−
1
+
3g
454, 1379 cm ; MS FAB: (m/z) 504 (MH , 78), 249
(2-naphthyl)-1-propanol 7F: OD column (hexane/i-
(
100), 221 (24), 193 (35); HR-MS (FAB+) calcd for
PrOH 96/4, flow rate: 1 ml/min); (R)-7F 19.6 min,
+
3g
C H FeNO (MH ): 504.1837. Found: 504.1847.
(S)-7F 15.4 min. For trans-1-phenyl-1-penten-3-ol 7G:
2
8
34
4