Enantioselective Cyclopropanation of Allylic Alcohols
J . Org. Chem., Vol. 62, No. 3, 1997 593
(
2
dd, J ) 6.3, J ) 11.5, 1 H), 3.46 (dd, J ) 8.5, J ) 11.4, 1 H),
0.10 mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10
equiv), and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one
2 2
flask with CH I (161 µL, 2.00 mmol, 2.00 equiv) and dieth-
.71 (m, 2 H), 1.69 (m, 1 H), 1.49 (m, 1 H), 1.34 (bs, 1 H), 1.18
1
3
(s, 3 H); C NMR (100 MHz) 142.42, 128.36, 128.30, 125.70,
6
(
9
3.72, 42.98, 33.19, 26.17, 19.92, 17.60, 17.06; MS (EI) 190
ylzinc (103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 186 mg (98%) of 27 after flash chromatography
(hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a clear,
colorless oil (reaction time of 90 min): bp 80 °C (0.01 Torr);
+
26
M , 5); IR 3344 (s); [R]
D
) -19.2° (CHCl
3
, c ) 5.00); GC t
(1R*,2R*)-23 7.6
R
.1 min (HP-5, isothermal 200 °C); HPLC t
R
min (89.3%); t
AD, hexane/EtOH, 95/5, 1.0 mL/min); TLC R
EtOAc, 3/1). Anal. Calcd for C13 18O (190.29): C, 82.06; H,
.53. Found: C, 81.91; H, 9.47.
1R*,2S*)-2-Meth yl-2-(2-ph en yleth yl)cyclopr opan em eth -
a n ol (24). Following protocol I, from 176 mg (1.00 mmol) of
Z)-3-methyl-5-phenyl-2-pentenol (8), promoter 16 (27 mg, 0.10
R
(1S*,2S*)-23 9.0 min (10.7%) (79% ee) (Daicel
1
f
0.25 (hexane/
H NMR (400 MHz) 7.32-7.25 (m, 2 H), 7.22-7.16 (m, 3 H),
H
3.31 (q, J ) 11.0, 2 H), 2.71 (m, 2 H), 1.67 (m, 2 H), 1.46 (bs,
1 H), 1.11 (s, 3 H), 0.65 (m, 1 H), 0.54 (dd, J ) 4.5, J ) 8.1, 1
H), 0.02 (t, J ) 4.7, 1 H); 13C NMR (100 MHz) 142.28, 128.44,
128.27, 125.74, 72.44, 36.33, 30.96, 22.36, 21.49, 16.54, 15.22;
9
(
+
26
(
MS (EI) 190 (M , 4); IR 3347 (s); [R]
D
) -4.8° (CHCl , c )
3
mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10 equiv),
5.00); GC t 6.9 min (U2, isothermal 200 °C); HPLC tR
R
and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one flask
(1R*,2R*)-27 18.9 min (62.8%); tR (1S*,2S*)-27 16.4 min
(37.2%) (26% ee) (Daicel AD, hexane/EtOH, 99/1, 1.0 mL/min);
TLC R 0.30 (hexane/EtOAc, 3/1). Anal. Calcd for C H18O
2 2
with CH I (161 µL, 2.00 mmol, 2.00 equiv) and diethylzinc
(
103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 187 mg (98%) of 24 after flash chromatography
hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a clear,
f
13
(190.29): C, 82.06; H, 9.53. Found: C, 81.83; H, 9.59.
1R*,2S*)-1-Meth yl-2-(2-ph en yleth yl)cyclopr opan em eth -
a n ol (28). Following protocol I, from 176 mg (1.00 mmol) of
Z)-2-methyl-5-phenyl-2-pentenol (12), promoter 16 (27 mg,
.10 mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10
equiv), and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one
flask with CH (161 µL, 2.00 mmol, 2.00 equiv) and dieth-
(
(
colorless oil (reaction time of 30 min): bp 90 °C (0.01 Torr);
1
H NMR (400 MHz) 7.31-7.25 (m, 2 H), 7.21-7.15 (m, 3 H),
(
0
3
1
1
.65 (dd, J ) 7.0, J ) 11.3, 1 H), 3.56 (dd, J ) 8.0, J ) 11.4,
H), 2.72 (m, 2 H), 1.66 (dd, J ) 7.8, J ) 9.0, 2 H), 1.44 (bs,
H), 1.16 (s, 3 H), 0.97 (m, 1 H), 0.52 (dd, J ) 4.5, J ) 8.5, 1
2 2
I
1
3
H), 0.16 (t, J ) 4.9, 1 H); C NMR (100 MHz) 142.69, 128.33,
1
ylzinc (103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 171 mg (90%) of 28 after flash chromatography
28.29, 125.71, 63.44, 36.45, 33.59, 27.28, 24.38, 20.38, 17.52;
+
27
MS (EI) 190 (M , 7); IR 3342 (s); [R]
.00); GC t 9.6 min (HP-5, isothermal 200 °C); HPLC t
1R*,2S*)-24 19.1min (82.8%); t (1S*,2R*)-24 25.9 min (17.2%)
66% ee) (Daicel OD, hexane/EtOH, 99/1, 1.0 mL/min); TLC
0.25 (hexane/EtOAc, 3/1). Anal. Calcd for
190.29): C, 82.06; H, 9.53. Found: C, 81.94; H, 9.46.
1R*,2S*)-1-Meth yl-2-ph en ylcyclopr opan em eth an ol (25).
Following protocol I, from 148 mg (1.00 mmol) of (E)-2-methyl-
-phenyl-2-propenol (9), promoter 16 (27 mg, 0.10 mmol, 0.10
D
) +5.8° (CHCl
3
, c )
(hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a clear,
5
(
(
R
(
R
R
colorless oil (reaction time of 90 min): bp 80 °C (0.01 Torr);
R
1
H NMR (400 MHz) 7.32-7.25 (m, 2 H), 7.22-7.17 (m, 3 H),
3
1
.54 (d, J ) 11.3, 1 H), 3.39 (d, J ) 11.2, 1 H), 2.71 (m, 2 H),
f
13 18
C H O
.77 (m, 1 H), 1.63 (m, 1 H), 1.24 (bs, 1 H), 1.11 (s, 3 H), 0.70
(
m, 1 H), 0.47 (dd, J ) 4.4, J ) 8.3, 1 H)), 0.11 (t, J ) 5.1, 1
(
13
H); C NMR (100 MHz) 142.31, 128.48, 128.30, 125.79, 67.09,
3
+
6.43, 31.38, 24.67, 22.54, 22.25, 17.25; MS (EI) 190 (M , 5);
3
27
IR 3361 (s); [R]
D
) +21.6° (CHCl
HP-5, isothermal 200 °C); HPLC t
75.0%); t (1S*,2R*)-28 19.2 min (25.0%) (50% ee) (Daicel OJ ,
0.30 (hexane/EtOAc,
18O (190.29): C, 82.06; H, 9.53.
3
, c ) 5.00); GC t
R
R
8.9 min
(1R*,2S*)-28 23.5 min
equiv), zinc iodide (32 mg, 0.10 mmol, 0.10 equiv), and
(
(
diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one flask with
R
2 2
CH I (161 µL, 2.00 mmol, 2.00 equiv) and diethylzinc (103
hexane/EtOH, 99/1, 1.0 mL/min); TLC R
/1). Anal. Calcd for C13
Found: C, 81.98; H, 9.51.
f
µL, 1.00 mmol, 1.00 equiv) in the second flask was obtained
3
H
1
3
48 mg (91%) of 25 after flash chromatography (hexane/EtOAc,
/1) and bulb-to-bulb distillation as a clear, colorless oil
1
(1R*,2S*)-1,2-Dim et h yl-2-p h en ylcyclop r op a n em et h a -
n ol (29). Following protocol I, from 162 mg (1.00 mmol) of
(reaction time of 300 min): bp 60 °C (0.005 Torr); H NMR
(
400 MHz) 7.32-7.25 (m, 2H), 7.23-7.16 (m, 3 H), 3.55 (t, J
(E)-2,3-dimethyl-3-phenyl-2-propenol (13), promoter 16 (27 mg,
)
0
1
11.1, 2 H), 2.05 (dd, J ) 5.9, J ) 8.6, 1 H), 1.88 (bs, 1 H),
.91 (m, 2 H), 0.89 (s, 3 H); 13C NMR (100 MHz) 138.76, 129.05,
27.95, 125.84, 71.69, 26.68, 25.11, 15.73, 15.08; MS (EI) 162
0.10 mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10
equiv), and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one
2 2
flask with CH I (161 µL, 2.00 mmol, 2.00 equiv) and dieth-
ylzinc (103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 150 mg (85%) of 29 after flash chromatography
+
27
(
9
2
M , 6); IR 3345 (s); [R]
D
) -1.4° (CHCl
.1 min (HP-5, isothermal 170 °C); HPLC t
8.2min (48.7%); t (1S*,2R*)-25 13.3 min (44.2%) (5% ee)
0.40
14O (162.26): C,
3
, c ) 5.00); GC t
R
R
(1R*,2S*)-25
R
(hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a low-
(
(
8
Daicel AD, hexane/EtOH, 98/2, 1.0 mL/min); TLC R
hexane/EtOAc, 3/1). Anal. Calcd for C11
1.44; H, 8.70. Found: C, 81.18; H, 8.72.
1R*,2R*)-1-Met h yl-2-p h en ylcyclop r op a n em et h a n ol
26). Following protocol I, from 148 mg (1.00 mmol) of (Z)-2-
f
melting solid (reaction time of 90 min): bp 70 °C (0.06 Torr);
H
1
H NMR (400 MHz) 7.33-7.16 (m, 5 H), 3.84 (d, J ) 11.2, 1
H), 3.70 (d, J ) 11.5, 1 H), 1.60 (bs, 1 H), 1.47 (s, 3 H), 0.93 (d,
J ) 4.9, 1 H), 0.84 (s, 3 H), 0.77 (d, J ) 4.9, 1 H); C NMR
(
1
3
(
(
2
)
2
2
1
100 MHz) 144.98, 129.00, 128.14, 125.84, 68.28, 30.92, 27.26,
methyl-3-phenyl-2-propenol (10), promoter 16 (27 mg, 0.10
mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10 equiv),
and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one flask
+
27
3.45, 23.34, 19.88; MS (EI) 176 (M , <1); IR 3261 (s); [R]
-9.6° (CHCl , c ) 2.40); GC t 6.4 min (HP-5, isothermal
00 °C); HPLC t (1R*,2S*)-29 13.4 min (70.2%); t (1S*,2R*)-
9 15.5 min (28.7%) (43% ee) (Daicel AD hexane/EtOH, 97/3,
.0 mL/min); TLC R 0.30 (hexane/EtOAc, 3/1). Anal. Calcd
16O (176.26): C, 81.75; H, 9.18. Found: C, 81.74; H,
D
3
R
R
R
with CH
103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 157 mg (97%) of 26 after flash chromatography
hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a clear,
2 2
I (161 µL, 2.00 mmol, 2.00 equiv) and diethylzinc
(
f
for C12
.20.
(1R*,2R*)-1,2-Dim eth yl-2-p h en ylcyclop r op a n em eth a -
H
(
9
colorless oil (reaction time of 300 min): bp 80 °C (0.01 Torr);
1
H NMR (400 MHz) 7.31-7.25 (m, 2 H), 7.24-7.16 (m, 3 H),
3
6
0
1
.36 (d, J ) 11.5, 1 H), 3.22 (d, J ) 11.6, 1 H,), 2.06 (dd, J )
.3, J ) 8.3), 1.34 (s, 3 H), 1.25 (bs, 1 H), 1.05 (t, J ) 5.5, 1 H),
.83 (dd, J ) 5.1, J ) 8.3, 1 H); 13C NMR (100 MHz) 138.76,
28.52, 128.29, 126.07, 66.84, 29.12, 25.42, 22.34, 15.58; MS
n ol (30). Following protocol I, from 162 mg (1.00 mmol) of
(Z)-2,3-dimethyl-3-phenyl-2-propenol (14), promoter 16 (27 mg,
0.10 mmol, 0.10 equiv), zinc iodide (32 mg, 0.10 mmol, 0.10
equiv), and diethylzinc (113 µL, 1.10 mmol, 1.10 equiv) in one
+
28
(
EI) 162 (M , 6); IR 3372 (s); [R]
D
) +1.4° (CHCl
6.6 min (U2, isothermal 170 °C); HPLC t (1R*,2R*)-26
(1S*,2S*)-26 15.8 min (45.2%) (10% ee)
Daicel OJ , hexane/EtOH, 99/1, 1.0 mL/min); TLC R 0.35
hexane/EtOAc, 3/1). Anal. Calcd for C11 14O (162.26): C,
1.44; H, 8.70. Found: C, 81.28; H, 8.75.
1R*,2R*)-1-Meth yl-2-(2-ph en yleth yl)cyclopr opan em eth -
a n ol (27). Following protocol I, from 176 mg (1.00 mmol) of
E)-2-methyl-5-phenyl-2-pentenol (11), promoter 16 (27 mg,
3
, c ) 5.00);
2 2
flask with CH I (161 µL, 2.00 mmol, 2.00 equiv) and dieth-
GC t
1
(
(
8
R
R
ylzinc (103 µL, 1.00 mmol, 1.00 equiv) in the second flask was
obtained 150 mg (85%) of 30 after flash chromatography
(hexane/EtOAc, 3/1) and bulb-to-bulb distillation as a clear,
colorless solid (reaction time of 90 min): bp 50 °C (0.005 Torr);
9.4 min (54.8%); t
R
f
H
1
H NMR (400 MHz) 7.31-7.25 (m, 4 H), 7.21-7.16 (m, 1 H),
(
3.15 (d, J ) 11.4, 1 H), 3.06 (d, J ) 11.3, 1 H), 1.42 (s, 3 H),
1.37 (s, 3 H), 1.36 (bs, 1 H), 1.10 (d, J ) 4.9, 1 H), 0.48 (d, J )
4.9, 1 H); 13C NMR (100 MHz) 144.91, 128.41, 126.06, 69.31,
(