1006
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Khanova et al.
Dibutyl 2ꢀ(transꢀ2ꢀphenylvinyl)ꢀ1,3ꢀdioxolaneꢀtransꢀ4,5ꢀ
dicarboxylate (2d). The yield was 70%, yellow oil, was isolated
by column chromatography, Rf 0.77 (petroleum ether—AcOEt,
7 : 3, as the eluent). Found (%): C, 67.08; H, 7.33. C21H28O6.
Calculated (%): C, 67.75; H, 7.37. IR, ν/cm–1: 694, 754, 964,
1090, 1144, 1210, 1576, 1624, 1678, 1744, 2872, 2932, 2956.
1H NMR, δ: 0.82—0.97 (m, 6 H, 2 Me); 1.33—1.45, 1.34—1.47,
and 4.17—4.29 (all m, 4 H each, 3 CH2); 4.77 and 4.87 (both d,
1 H each, H(4) and H(5), 3J = 3.7 Hz); 5.81 (d, 1 H, H(2), 3J =
6.7 Hz); 6.26 (dd, 1 H, H(1´), J = 16.0 Hz, J = 6.7 Hz); 6.84
(d, 1 H, H(2´), 3J = 16.0 Hz); 7.19—7.29 (m, 5 H, Ar).
13C NMR, δ: 13.4 (2 Me); 18.9 and 30.3 (2 CH2 each); 65.9
(2 OCH2); 72.0 and 77.3 (C(4) and C(5)); 107.0 (C(2)); 123.6
(C(1´)); 135.3 (C(2´)); 125.7—128.1 (5 CH, Ar); 135.3 (C, Ar);
169.5 (COO).
chromatographed on SiO2. The yields of the reaction products
are given in Table 1. The physicochemical and spectroscopic
characteristics of compounds 4,17 5,7 7,12 and 1015 are consisꢀ
tent with the published data.
4ꢀCyclopropylbutanꢀ2ꢀone (6). The product was isolated by
column chromatography, Rf 0.83 (petroleum ether—AcOEt,
20 : 1, as the eluent). Found (%): C, 74.90; H, 10.78. C7H12O.
Calculated (%): C, 74.95; H, 10.83. IR, ν/cm–1: 820, 910, 1126,
1
1258, 1378, 1456, 1672, 2854, 2926, 3076. H NMR, δ: –0.06
3
3
and 0.30 (both m, 2 H each, CH2CH2); 0.56 (m, 1 H, CH); 1.35
3
(q, 2 H, H2C(4), J = 7.2 Hz); 2.04 (s, 3 H, Me); 2.43 (t, 2 H,
H2C(3), 3J = 7.2 Hz). 13C NMR, δ: 4.5 (CH2CH2); 10.6 (CH);
29.0 (C(4)); 30.0 (C(1)); 43.8 (C(3)); 209.3 (C(2)).
Dibutyl 2ꢀ(transꢀ2ꢀmethylcyclopropyl)ꢀ1,3ꢀdioxolaneꢀtransꢀ
4,5ꢀdicarboxylate (8). The product was isolated by column chroꢀ
matography, Rf 0.80 (petroleum ether—AcOEt, 7 : 3, as the eluꢀ
ent). Found (%): C, 62.12; H, 8.54. C17H28O6. Calculated (%):
C, 62.18; H, 8.59. Compound 8 was prepared as a mixture of
two diastereomers in a ratio of 1 : 5 or 1 : 1.2 with the use of
Pd(acac)2 or Cu(OTf)2, respectively. The diastereomers are charꢀ
acterized by slightly different positions of the signals in the
13C NMR spectra. 1H NMR, δ: 0.36—0.42 and 0.62—0.70
(both m, 1 H each) and 0.81—0.90 (m, 2 H, protons of the
cyclopropane ring); 0.92 (t, 3 H, Me, 3J = 7.3 Hz); 1.05 (d, 3 H,
5,5ꢀDiethoxyhexꢀ1ꢀene (3b). The yield was 35%, colorless
liquid, b.p. 70 °C (40 Torr). Found (%): C, 69.65; H, 11.74.
C10H20O2. Calculated (%): C, 69.72; H, 11.70. IR, ν/cm–1
:
1
850, 916, 1054, 1126, 1216, 1252, 1372, 1642, 2974. H NMR,
3
δ: 1.17 and 1.23 (both t, 3 H each, Me, J = 7.1 Hz); 1.30 (s,
3 H, Me); 1.71—1.74 (m, 2 H, H2C(4)); 2.06—2.12 (m, 2 H,
3
H2C(3)); 3.45 and 3.71 (both q, 2 H each, CH2, J = 7.1 Hz);
2
3
4.95 (dd, 1 H, transꢀHC(1), J = 1.6 Hz, Jcis = 10.4 Hz); 5.25
2
3
(dd, 1 H, cisꢀHC(1), J = 1.6 Hz, Jtrans = 17.0 Hz); 5.83 (ddt,
1 H, HC=, 3J = 6.4 Hz, 3J = 10.4 Hz, 3J = 17.0 Hz). 13C NMR,
δ: 15.4, 18.2, and 22.0 (all Me); 28.6 (C(3)); 36.4 (C(4)); 55.5
(2 OCH2); 101.3 (C(5)); 114.2 (C(1)); 138.4 (C(2)).
3
3
Me, J = 5.6 Hz); 1.38 (sextet, 4 H, 2 CH2Me, J = 7.3 Hz);
1.59—1.70 (m, 4 H, 2 CH2); 4.19 (q, 4 H, 2 OCH2, 3J = 6.6 Hz);
4.61 (d, 1 H, H(5), 3J = 4.0 Hz); 4.71—4.76 (m, 2 H, H(4)
and H(2)).
2ꢀ(Butꢀ3ꢀenyl)ꢀ2ꢀmethylꢀ1,3ꢀdioxolane (3c). The yield was
34%, colorless liquid, b.p. 50 °C (20 Torr). Found (%): C, 67.67;
H, 9.86. C8H14O2. Calculated (%): C, 67.57; H, 9.92. IR,
ν/cm–1: 520, 628, 1054, 1126, 1372, 1450, 1642, 1720, 2878,
2944, 2980. 1H NMR, δ: 1.31 (s, 3 H, Me); 1.69—1.74 (m, 2 H,
H2C(1´)); 2.07—2.18 (m, 2 H, H2C(2´)); 3.89—3.95 (m, 4 H,
H2C(4) and H2C(5)); 4.91 (dd, 1 H, transꢀHC(1), 2J = 1.8 Hz,
Minor diastereomer (8a). 13C NMR, δ: 9.4 (HC(2´)); 9.6
(H2C(3´)); 13.4 and 17.7 (both Me); 18.8 (CH2Me); 20.9
(HC(1´)); 30.3 (CH2); 65.4 (OCH2); 76.4 (HC(4), HC(5));
110.4 (HC(2)); 169.7 (COO).
Major diastereomer (8b). 13C NMR, δ: 9.4 (HC(2´)); 9.6
(H2C(3´)); 13.4 and 17.8 (both Me); 18.8 (CH2Me); 21.0
(HC(1´)); 30.3 (CH2); 65.5 (OCH2); 76.7 (HC(4), HC(5));
110.6 (HC(2)); 169.1 (COO).
3Jcis = 10.2 Hz); 5.00 (dd, 1 H, cisꢀHC(1), 2J = 1.6 Hz, 3Jtrans
=
17.2 Hz); 5.82 (ddt, 1 H, =CH, 3J = 6.5 Hz, 3J = 10.2 Hz, 3J =
17.2 Hz). 13C NMR, δ: 23.7 (Me); 28.2 (C(2´)); 38.1 (C(3´));
64.5 (C(4) and C(5)); 109.6 (C(2)); 114.1 (=CH2); 138.4 (=CH).
Dibutyl 2ꢀ(butꢀ3ꢀenyl)ꢀ2ꢀmethylꢀ1,3ꢀdioxolaneꢀtransꢀ4,5ꢀ
dicarboxylate (3d). The yield was 30%, yellow liquid, b.p. 140 °C
(1 Torr). Found (%): C, 63.22; H, 8.89. C18H30O6. Calcuꢀ
transꢀ2ꢀ(Diethoxymethyl)ꢀ1ꢀphenylcyclopropane (9). The
product was isolated by column chromatography, Rf 0.77 (peꢀ
troleum ether—AcOEt, 20 : 1, as the eluent). Found (%):
C, 76.30; H, 9.21. C14H20O2. Calculated (%): C, 76.33; H, 9.15.
IR, ν/cm–1: 700, 754, 1060, 1120, 1372, 1444, 1498, 1606, 1654,
1
1
lated (%): C, 63.14; H, 8.83. H NMR, δ: 0.96 (t, 6 H, 2 Me,
2926, 2974. H NMR, δ: 0.91—1.03 (m, 2 H); 1.08—1.14 and
3J = 6.2 Hz); 1.35—1.46 (m, 4 H, 2 CH2); 1.48 (s, 3 H, Me);
1.63—1.74 (m, 4 H, 2 CH2); 1.83—1.89 (m, 2 H, CH2);
2.21—2.26 (m, 2 H, =CHCH2); 4.21—4.33 (m, 4 H, 2 OCH2);
4.71 and 4.80 (both d, 1 H each, H(4) and H(5), 3J = 6.2 Hz);
1.41—1.48 (both m, 1 H each, protons of the cyclopropane
ring); 1.21 and 1.23 (both t, 6 H, 2 Me, 3J = 6.8 Hz); 3.44—3.73
(m, 4 H, 2 OCH2); 4.43 (d, 1 H, CH(OEt)2, 3J = 4.8 Hz);
7.07—7.28 (m, 5 H, Ar). 13C NMR, δ: 12.4 (CH2); 15.3 (Me);
19.4 and 25.4 (2 CH of the cyclopropane ring); 60.8 and
61.2 (2 OCH2); 102.7 (CH(OEt)2); 125.5—128.6 (5 CH, Ar);
142.4 (C, Ar).
2
3
4.95 (dd, 1 H, transꢀHC(1), J = 1.6 Hz, Jcis = 10.3 Hz); 5.03
2
3
(dd, 1 H, cisꢀHC(1), J = 1.6 Hz, Jtrans = 17.0 Hz); 5.83 (ddt,
1 H, =CH, 3J = 6.5 Hz, 3J = 10.3 Hz, 3J = 17.0 Hz). 13C NMR,
δ: 13.5 (2 Me); 17.5 (Me); 18.9 (2 CH2Me); 30.4 (2 CH2); 65.1
(2 OCH2); 72.0 and 76.6 (C(4) and C(5)); 107.3 (C(2)); 116.0
(=CH2); 134.8 (=CH); 171.5 (COO).
Dibutyl 2ꢀ(2ꢀtransꢀphenylcyclopropyl)ꢀ1,3ꢀdioxolaneꢀtransꢀ
4,5ꢀdicarboxylate (11). Yellow liquid, b.p. 209 °C (0.1 Torr).
Found (%): C, 67.78; H, 7.78. C22H30O6. Calculated (%):
C, 67.70; H, 7.74. IR, ν/cm–1: 694, 754, 964, 1090, 1144, 1210,
1576, 1624, 1678, 1744, 2872, 2932, 2956. Compound 11 was
prepared as a mixture of two diastereomers in a ratio of 1 : 10
with the use of Pd(acac)2, The diastereomers are characterized
by slightly different positions of the signals in the NMR spectra.
Cyclopropanation of unsaturated carbonyl compounds and
their derivatives (general procedure). A 0.45—0.47 M CH2N2
solution in Et2O (45 mL, ~21 mmol) was added with stirring to a
solution of a carbonyl compound or its derivative (7.0 mmol)
and Pd(acac)2 (0.042 g, 0.14 mmol) in Et2O (20 mL) (or
Cu(OTf)2 (0.051 g, 0.14 mmol) in CH2Cl2 (20 mL)) at 5—10 °C
for 30 min. The reaction mixture was additionally stirred for
30—40 min and passed through a thin layer of Al2O3. The solꢀ
vent was removed in low vacuum. The residue was distilled or
3
1H NMR, δ: 1.08 (t, 3 H, Me, J = 7.3 Hz); 1.10 (t, 3 H, Me,
3J = 7.2 Hz); 1.19 and 1.37 (both m, 1 H each, H2C(3´)); 1.54
(sextet, 4 H, 2 CH2Me, 3J = 7.3 Hz); 1.74—1.84 (m, 4 H,
2 CH2); 2.24—2.34 (m, 2 H, HC(1´) and HC(2´)); 4.33—4.39