9146
L.O. Khafizova et al. / Tetrahedron 67 (2011) 9142e9147
3
1
.15 (dd, 2J¼6.0 Hz, J¼10.0 Hz, 1H, CH
2
cyclopropane ring);
); 2.01
4.2.6.2. (trans)-1-Ethoxy-1-methyl-2-(1-naphthyl)cyclopropane
1
1.36e1.39 (m, 1H, CH
2
cyclopropane ring); 1.60 (s, 3H, CH
3
(trans-1k). H NMR (400 MHz, CDCl
3
):
d
1.07 (s, 3H, CH
3
); 1.13 (dd,
3
3
2
3
(
(
dd,
J
trans¼6.0 Hz,
J
cis¼10.0 Hz, 1H, CH cyclopropane ring); 3.15
J¼7.0 Hz, J¼9.0 Hz, 1H, CH
2
cyclopropane ring); 1.59 (t, J¼7.0 Hz,
2
3
2
3
3
dq, J¼9.0 Hz, J¼7.0 Hz, 1H, CH
2
eOe); 3.58 (dq, J¼9.0 Hz,
1H, CH
2
cyclopropane ring); 2.48 (dd,
J
trans¼7.0 Hz,
J
cis¼9.0 Hz,
3
13
2
3
J¼7.0 Hz, 1H, CH
100 MHz, CDCl ):
26.9 (2C), 126.9 (2C), 127.0 (2C), 127.1 (2C), 128.1 (2C), 128.8 (2C),
28.8 (2C), 129.0 (2C), 137.9 (2C), 138.2, 138.2, 138.9 (2C), 141.0 (2C),
41.2 (2C) arom (cis/trans)] ppm.
2
eOe); 7.28e7.69 (m, 4H, Ph) ppm. C NMR
1H, CH); 3.67 (dq, J¼9.0 Hz, J¼7.0 Hz, 1H, CH
2
); 3.84 (dq,
2
3
13
(
1
1
1
3
d
15.4, 21.3, 21.7, 30.4, 62.3, 63.1 [126.4 (2C),
J¼9.0 Hz, J¼7.0 Hz, 1H, CH
2
); 7.20e8.39 (m, 7H, arom) ppm.
C
NMR (100 MHz, CDCl
3
):
d
15.9, 16.2, 17.1, 28.1, 61.9, 62.6 [124.3,
124.6, 125.0, 125.1, 125.3, 125.3, 125.4, 125.8, 125.8, 126.0, 126.4,
126.9, 12.3, 128.6, 133.5, 133.5, 133.9, 134.0, 134.3, 135.6 arom (cis/
trans)] ppm.
4
.2.4.2. (trans)-1-Ethoxy-1-methyl-2-(4-phenylphenyl)cyclopro-
1
2
pane (trans-1i). H NMR (400 MHz, CDCl
3
):
d
1.04 (dd, J¼6.0 Hz,
0
4
.3. The reaction of styrene and EtAlCl
2
( or Et
2
AlCl), RCO
2
R in
3
J¼10.0 Hz, 1H, CH
2 3
cyclopropane ring); 1.15 (s, 3H, CH ); 1.25 (t,
i
the presence of Ti(O Pr)
4
(general procedure)
J¼7.0 Hz, 3H, CH
3
); 1.28 (t, J¼6.0 Hz, 1H, CH
2
); 1.90 (dd,
3
3
J
trans¼6.0 Hz, Jcis¼10.0 Hz, 1H, CH cyclopropane ring); 2.35 (s, 3H,
The calcined and argon-filled 50 mL glass reactor equipped with
13
CH
3
); 3.65 (q, J¼7.0 Hz, 2H, CH
): 15.7, 16.1, 17.9, 21.0, 29.3, 61.8, 62.3 [126.4
2C), 126.9 (2C), 126.9 (2C), 127.0 (2C), 127.1 (2C), 128.1 (2C), 128.8
2
); 7.06e7.21 (m, 4H, Ph) ppm.
C
i
magnetic stirrer was charged with THF (5 mL), Ti(O Pr)
4
(1 mmol),
NMR (100 MHz, CDCl
3
d
magnesium (powder) (15 mmol), styrene (10 mmol), ethyl acetate
(
(
(
(
10 mmol), and EtAlCl
2
(or Et
2
AlCl) (20 mmol) under a dry argon
2C), 128.8 (2C), 129.0 (2C), 137.9 (2C), 138.2, 138.2, 138.9 (2C), 141.0
2C), 141.2 (2C) arom (cis/trans)] ppm.
ꢀ
atmosphere at 0 C. The reaction mixture was allowed to warm to rt
(
ꢀ
20e22 C) and stirred for 10 h. Upon completion of the reaction
and addition of hexane (5 mL), the reaction mixture was treated
with 5e8% HCl solution. The organic layer was separated. The
aqueous solution was extracted (10 mLꢂ2) by diethyl ether. The
resultant ether extract was combined with the organic layer, then
4
.2.5. (cis/trans)-1-Ethoxy-1-methyl-2-(2-methoxylphenyl)cyclopro-
pane (1j). R
m/z: 206 [M] . Anal. Calcd for C13
C, 75.58; H, 8.72%.
f
0.70 (hexane/ethyl acetate, 1:1) (0.91 g, 44% yield). MS
þ
H
18
O
2
: C, 75.69; H, 8.80%. Found:
was neutralized with Na
end products were purified by column chromatography on silica gel
SiO (40e100 mesh grade, hexane/ethyl acetate 50:1 as eluent) and
identified by means of spectral methods.
2 3 4
CO to pH w7 and dried over MgSO . The
4
.2.5.1. (cis)-1-Ethoxy-1-methyl-2-(2-methoxylphenyl)cyclopro-
1
2
pane (cis-1j). H NMR (400 MHz, CDCl
CH cyclopropane ring); 1.31 (dd,
); 1.00 (t, J¼6.0 Hz, 1H, CH
cyclopropane ring); 1.59 (s, 3H, CH );
3
):
d
0.88 (t, J¼7.0 Hz, 3H,
3
2
2
3
J¼6.0 Hz, J¼10.0 Hz, 1H, CH
2
3
4
1
CH
7
.3.1.
:1) (0.55 g, 37% yield). H NMR (400 MHz, CDCl
, J¼7.0 Hz); 1.29e1.83 (m, 4H, 2CH ), 4.67 (t, 1H, CH, J¼6.0 Hz);
.27e7.36 (m, 5H, CHePh) ppm. C NMR (100 MHz, CDCl ): 14.0,
9.0, 41.2, 74.4, 125.9, 127.5 (2C), 128.4 (2C), 145.0 ppm. MS m/z: 150
a
-Propylbenzenemethanol (2). R
f
0.47 (hexane/ethyl acetate,
3
3
2
.37 (dd,
J
trans¼6.0 Hz,
J
cis¼10.0 Hz, 1H, CH cyclopropane ring);
1
): 0.95 (t, 3H,
d
3
.02 (dq, 2J¼9.0 Hz, J¼7.0 Hz, 1H, CH
3
2
eOe); 3.49 (dq, J¼9.0 Hz,
eOe, (cis/trans))];
): 15.3, 19.1
1.6, 25.3 [55.2, 55.6 (cis/trans)], 62.0, 62.7 [110.1 (2C), 120.0, 120.2,
26.3 (2C), 127.1, 127.2, 128.2 (2C), 158.5, 159.4 arom (cis/trans)]
ppm.
2
3
3
3
2
J¼7.0 Hz, 1H, CH
2 3
eOe) [3.89, 3.90 (s, 6H, CH
13
d
13
3
6
.87e7.23 (m, 4H, Ph) ppm. C NMR (100 MHz, CDCl
3
d
1
2
1
þ
[M] . Anal. Calcd for C10
H14O: C, 76.96; H, 9.39%. Found: C, 79.84; H,
8.92%.
4
.2.5.2. (trans)-1-Ethoxy-1-methyl-2-(2-methoxylphenyl)cyclo-
4.4. Cyclopropanation of alkyl-substituted
diolefins) mediated by EtAlCl (or Et
as a catalyst (general procedure)
a
-olefins (or
a
,
u
-
1
2
0
propane (trans-1j). H NMR (400 MHz, CDCl
3
):
d
0.95 (dd, J¼7.0 Hz,
2
2
AlCl), RCO
2
R and Cp
2
ZrCl
2
3
J¼9.0 Hz, 1H, CH
2 3
cyclopropane ring); 1.12 (s, 3H, CH ); 1.27 (t,
J¼7.0 Hz, 3H, CH ); 1.35 (t, J¼6.0 Hz, 1H, CH
3
2
cyclopropane ring);
3
3
2
.30 (dd, Jtrans¼7.0 Hz, Jcis¼9.0 Hz,1H, CH cyclopropane ring); 3.72
The calcined and argon-filled 50 mL glass reactor equipped with
magnetic stirrer was charged with THF (5 mL), Cp ZrCl catalyst
(1 mmol), magnesium (powder) (15 mmol), the corresponding
alkyl-substituted -olefin (10 mmol), alkyl carboxylate (10 mmol;
-diolefin), and EtAlCl (or Et AlCl) (20 mmol;
2
3
2
(
dq, J¼9.0 Hz, J¼7.0 Hz, 1H, CH
2
eOe); 3.82 (dq, J¼9.0 Hz,
2
2
3
J¼7.0 Hz, 1H, CH
.87e7.23 (m, 4H, Ph) ppm. C NMR (100 MHz, CDCl
7.8, 24.1 [55.2, 55.6 (cis/trans)], 61.6, 62.2 [110.1 (2C), 120.0, 120.2,
26.3 (2C), 127.1, 127.2, 128.2 (2C), 158.5, 159.4 arom (cis/trans)]
ppm.
2
eOe) [3.89, 3.90 (s, 6H, CH
3
eOe, (cis/trans))];
13
6
1
1
3
): d 15.9, 16.0,
a
20 mmol for
40 mmol for
a
,
u
2
2
a
,u
-diolefin) and AlCl
3
(20 mmol; 40 mmol for
a
,
u
-
ꢀ
diolefin) under a dry argon atmosphere at 0 C. The reaction mix-
ꢀ
ture was allowed to warm to rt (20e22 C) and stirred for additional
4
(
3
.2.6. (cis/trans)-1-Ethoxy-1-methyl-2-(1-naphthyl)cyclopropane
1k). R 0.68 (hexane/ethyl acetate, 1:1) (1.09 g, 48% yield). IR
430, 3046, 2974, 2927, 2871, 1925, 1580, 1509, 1402, 1219, 1126,
10 h. Upon completion of the reaction and addition of hexane
(5 mL), the reaction mixture was treated with 5e8% HCl solution.
The organic layer was separated. The aqueous solution was
extracted (10 mLꢂ2) by diethyl ether. The resultant ether extract
was combined with the organic layer, then was neutralized with
f
n
ꢁ
1
þ
1068, 1021, 778 cm . MS m/z: 226 [M] . Anal. Calcd for C16
H18O: C,
8
4.91; H, 8.02%. Found: C, 84.79; H, 7.95%.
Na
2
CO
3
to pH w7 and dried over MgSO
4
. The end products were
(40e100
4
.2.6.1. (cis)-1-Ethoxy-1-methyl-2-(1-naphthyl)cyclopropane
purified by column chromatography on silica gel SiO
2
1
(
cis-1k). H NMR (400 MHz, CDCl
.07 (t, J¼6.0 Hz, 1H, CH cyclopropane ring); 1.45 (dd, J¼6.0 Hz,
cyclopropane ring); 1.74 (s, 3H, CH ); 2.76 (dd,
cis¼10.0 Hz, 1H, CH cyclopropane ring); 2.95 (dq,
3
):
d
0.70 (t, J¼7.2 Hz, 3H, CH
3
);
mesh grade, hexane/ethyl acetate 4:1 as eluent) and identified by
means of spectral methods.
2
1
2
3
3
2
J¼10.0 Hz, 1H, CH
2
3
3
J
trans¼6.0 Hz,
J
4.4.1. (cis)-1-Methyl-2-hexylcyclopropanol (4a). R
f
0.55 (hexane/
3360 (OH), 3070 (CeH,
2
cyclopropane ring) cm . H NMR d 0.036 (t, 1H, CH , cyclopropane
3
2
3
J¼9.0 Hz, J¼7.0 Hz, 1H, CH
2
); 3.36 (dq, J¼9.0 Hz, J¼7.0 Hz, 1H,
ethyl acetate, 1:1) (0.66 g, 42% yield). IR n
13
ꢁ1 1
CH
2
); 7.20e8.39 (m, 7H, arom) ppm. C NMR (100 MHz, CDCl
3
):
2
3
d
15.3, 18.2, 21.8, 28.5, 62.2, 62.7 [124.3, 124.6, 125.0, 125.1, 125.3,
25.3, 125.4, 125.8, 125.8, 126.0, 126.4, 126.9, 128.3, 128.6, 133.5,
ring, J z J¼6.0 Hz); 0.80e1.16 (m, 5H, CH, H-C-H (cyclopropane
13
1
ring), CH
3 2 3
); 1.18e1.35 (m, 10H, 5CH ), 1.39 (s, 3H, CH ). C NMR
133.5, 133.9, 134.0, 134.3, 135.6 arom (cis/trans)] ppm.
(100 MHz, CDCl
3
): d 14.1, 20.2, 20.5, 22.6, 25.6, 29.2, 29.7, 29.9, 31.8,