Kaori Ambe-Suzuki et al.
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(EI, 70 eV): m/z (%)=256 (3) [M+], 122 (100); HR-MS
(70 eV, EI): m/z=256.1314, calcd. for C13H20O5 [M+]:
256.1311.
CH), 3.69 (s, 3H, OCH3), 3.72 (s, 3H, OCH3), 5.20 (t, J=
7.1 Hz, 1H, =CH), 5.75–5.79 (m, 1H, =CH), 5.83 (dt, J=
10.0, 3.0 Hz, 1H, =CH); 13C NMR (125 MHz, CDCl3): d
22.6, 23.4, 23.7, 30.1, 39.3, 40.5, 42.7, 43.8, 52.7, 52.9, 63.2
(CH3, CH2, and C), 122.1, 127.0, 127.3, 140.9 (=CH and =C),
170.4, 172.1, 208.6 (C=O); IR (neat): n=2950, 1730 (nCO),
1440, 1260 cmÀ1; DI-MS (EI, 70 eV): m/z (%)=320 (0.7)
[M+], 262 (39) [M+ÀCO2Me], 143 (100); HRMS (70 eV,
EI): m/z calcd for C17H21O4: 289.1440; found: 289.1463
[M+ÀOMe].
Compound (4): White solid; mp 145–1468C; Rf =0.20
(hexane/AcOEt=2:1); 1H NMR (500 MHz, CDCl3): d=
1.21–1.25 (m, 1H, one of CH2), 1.32 (dt, J=12.6, 11.9 Hz,
1H, one of CH2), 1.50–1.58 (m, 1H, one of CH2), 1.61 (s,
3H, CH3), 1.81 (dd, J=13.5, 5.5 Hz, 1H, one of CH2), 2.03–
2.09 (m, 1H, one of CH2), 2.14 (s, 3H, CH3), 2.31–2.37 (m,
1H, one of CH2), 2.42–2.47 (m, 2H, CH2), 2.56 (d, J=
13.6 Hz, 1H, one of CH2), 2.63 (d, J=13.6 Hz, 1H, one of
CH2), 2.65–2.73 (m, 2H, CH x 2), 2.79 (d, J=16.5 Hz, 1H,
one of CH2), 2.87 (d, J=16.5 Hz, 1H, one of CH2), 3.29 (dt,
J=7.3, 10.6 Hz, 1H, CH), 3.38 (t, J=8.8 Hz, 1H, CH), 3.68
(s, 3H, OCH3), 3.69 (s, 3H, OCH3), 3.70 (s, 3H, OCH3),
3.71 (s, 3H, OCH3), 4.63 (s, 1H, one of =CH2), 4.66 (s, 1H,
one of =CH2); 13C NMR (125 MHz, CDCl3): d=18.2 (CH3),
28.1, 29.1 (CH2), 29.9 (CH3), 32.6, 35.4, 38.6, 41.4 (CH), 41.4
(CH2), 43.2, 47.9, 48.2, 52.5, 52.55, 52.57, 52.7 (OCH3), 58.5,
61.1 (C), 110.5 (=CH2), 128.1, 132.8, 144.0 (=C), 170.6,
170.99, 171.02, 172.2, 208.4 (C=O); IR (KBr): n=2950, 1730
(CO), 1440, 1270, 1250, 1210, 1160 cmÀ1; DI-MS (EI, 70 eV):
m/z (%)=504 (48) [M+], 413 (100); HR-MS (70 eV, EI):
m/z=504.2343, calcd. for C27H36O9 [M+]: 504.2359.
(3Z,3aS*,6aR*)-Diethyl 3,3a,6,6a-tetrahydro-3-(5-oxohex-
an-2-ylidene)pentalene-1,1(2H)-dicarboxylate (6): Colorless
oil; Rf =0.23 (hexane/AcOEt=5:1; 1H NMR (500 MHz,
CDCl3): d=1.21 (t, J=7.2 Hz, 3H, CH3), 1.25 (t, J=7.2 Hz,
3H, CH3), 1.58 (s, 3H, CH3), 2.02–2.08 (m, 1H, one of
CH2), 2.15 (s, 3H, CH3), 2.23–2.30 (m, 1H, one of CH2),
2.32–2.54 (m, 4H, CH2 ꢁ2), 2.76- 2.83 (m, 2H, CH2), 3.48–
3.53 (m, 1H, CH), 3.85 (d, J=7.9 Hz, 1H, CH), 4.16 (q, J=
7.2 Hz, 2H, OCH2), 4.20 (q, J=7.2 Hz, 2H, OCH2), 5.56–
5.60 (m, 2H, =CH); NOESY cross peaks were detected: d=
1.58 vs. 2.76–2.83, 3.48–3.53 vs. 3.85; 13C NMR (125 MHz,
CDCl3): d=14.1, 14.2, 18.5 (CH3), 28.8 (CH2), 29.9 (CH3),
35.4, 35.8, 42.1 (CH2), 45.8, 53.0 (CH), 61.2, 61.3 (OCH2),
63.1 (C), 125.9, 129.2, 131.8, 135.2 (=C), 170.5, 171.7, 208.6
(C=O); IR (neat): n=2980, 1730 (CO), 1260 cmÀ1; DI-MS
(EI, 70 eV): m/z (%)=348 (6) [M+], 216 (100); HR-MS
(70 eV, EI): m/z=348.1923, calcd. for C20H28O5 [M+]:
348.1937.
Diethyl 2-(3-oxobutyl)-2-propylmalonate (7): Colorless
oil; Rf =0.23 (hexane/AcOEt=5:1); 1H NMR (500 MHz,
CDCl3): d=0.92 (t, J=7.3 Hz, 3H, CH3), 1.17–1.23 (m, 2H,
CH2), 1.25 (t, J=7.1 Hz, 6H, CH3), 1.81–1.85 (m, 2H, CH2),
2.12–2.16 (m, 2H, CH2), 2.14 (s, 3H, CH3), 2.41–2.44 (m,
2H, CH2), 4.15–4.21 (m, 4H, OCH2); 13C NMR (125 MHz,
CDCl3): d=14.0, 14.3 (CH3), 17.4, 26.4 (CH2), 29.8 (CH3),
35.5, 38.7 (CH2), 56.7 (C), 61.1 (OCH2), 171.4, 207.3 (C=O);
IR (neat): n=2970, 1730 (CO), 1220 cmÀ1; DI-MS (EI,
70 eV): m/z (%)=272 (0) [M+], 257 (6) [M+ÀMe], 173
(100); elemental analysis calcd. (%) for C14H24O5: C 61.74,
H 8.88; found: C 61.73, H 9.04.
(3Z)-Dimethyl 3,3a,7,7a-tetrahydro-3-(4-oxopentylidene)-
2H-indene-1,1(6H)-dicarboxylate (9a): Colorless oil; Rf =
0.29 (hexane/AcOEt=4/1); 1H NMR (500 MHz, CDCl3):
d=1.13–1.20 (m, 1H, one of CH2), 1.35–1.40 (m, 1H, one of
CH2), 1.90–2.03 (m, 2H, CH2), 2.11 (s, 3H, CH3), 2.30 (q,
J=7.1 Hz, 2H, CH2), 2.45 (t, J=7.1 Hz, 2H, CH2), 2.60 (d,
J=16.0 Hz, 1H, one of CH2), 2.90–2.95 (m, 1H, CH), 3.19
(dquint, J=16.0, 2.5 Hz, 1H, one of CH2), 3.32–3.38 (m, 1H,
(3Z)-Dimethyl 3,3a,7,7a-tetrahydro-3-(4-oxohexylidene)-
2H-indene-1,1(6H)-dicarboxylate (9b): Colorless oil; Rf =
0.46 (hexane/AcOEt=4/1); 1H NMR (500 MHz, CDCl3):
d=0.98 (t, J=7.2 Hz, 3H, CH3), 1.07–1.15 (m, 1H, one of
CH2), 1.31–1.34 (m, 1H, one of CH2), 1.87–1.98 (m, 2H,
CH2), 2.23–2.27 (m, 2H, CH2), 2.34 (q, J=7.2 Hz, 2H, CH2),
2.37 (t, J=7.2 Hz, 2H, CH2), 2.55 (d, J=15.8 Hz, 1H, one
of CH2), 2.84–2.89 (m, 1H, CH), 3.14 (dt, J=15.8, 2.4 Hz,
1H, one of CH2), 3.28 (s, 1H, CH), 3.63 (s, 3H, CH3), 3.66
(s, 3H, CH3), 5.15 (t, J=7.2 Hz, 1H, =CH), 5.69–5.73 (m,
1H, =CH), 5.77 (dt, J=10.0, 3.0 Hz, 1H, =CH); 13C NMR
(125 MHz, CDCl3): d=3.9, 14.3, 16.4, 19.3, 27.3, 40.5, 56.2,
56.7, 61.5, 68.9 (CH3, CH2, CH and C), 75.9, 82.2, 128.2,
ꢀ
133.1 ( C and =CH), 171.5, 171.7 (C=O); IR (neat): n=
2950, 1730 (C=O), 1260 cmÀ1; DI-MS (EI, 70 eV): m/z
(%)=334 (1.0) [M+], 303 (3) [M+ÀOMe], 202 (100); HR-
MS (70 eV, EI): m/z=303.1594, calcd. for C18H23O4 [M+]:
303.1596.
(3Z)-Dimethyl 3,3a,7,7a-tetrahydro-3-(4-oxohexylidene)-
2H-indene-1,1(6H)-dicarboxylate (9c): Colorless oil; Rf =
0.34 (hexane/AcOEt=4/1); 1H NMR (500 MHz, CDCl3):
d=1.03 (1.06) (d, J=7.0 Hz, 3H, CH3), 1.12–1.19 (m, 1H,
one of CH2), 1.37–1.39 (m, 1H, one of CH2), 1.89–2.02 (m,
2H, CH2), 2.08 (2.11) (s, 3H, OCH3), 2.34–2.37 (m, 1H,
CH), 2.47–2.59 (m, 2H, CH2), 2.62–2.64 (m, 1H, one of
CH2), 2.92–2.94 (m, 1H, CH), 3.18 (d, J=15.7 Hz, 1H, one
of CH2), 3.31–3.35 (m, 1H, CH), 3.67 (s, 3H, CH3), 3.70 (s,
3H, CH3), 5.16–5.19(m, 1H, =CH), 5.79–5.82 (m, 2H,
=CHꢁ2); 13C NMR (125 MHz, CDCl3): d=15.7, (16.5),
22.6, 23.7, 28.2, 31.7, (32.2), 39.4, 40.3, 42.7, 47.4, (47.6), 2.6,
52.9, 63.2 (CH3, CH2, CH and C), 120.8, 126.9, 127.3, 141.6
(=C and =CH), 170.3, 171.9 , 212.4 (C=O); IR (neat): n=
2950, 1730 (C=O), 1430, 1260, 1200 cmÀ1; DI-MS (EI,
70 eV): m/z (%)=334 (0) [M+], 303 (3) [M+ÀOMe], 202
(100); HR-MS (70 eV, EI): m/z=303.1597, calcd. for
C18H23O4: 303.1596 [M+ÀOMe].
(3Z)-Dimethyl 3,3a,7,7a-tetrahydro-3-(4-oxohexylidene)-
2H-indene-1,1(6H)-dicarboxylate (9d): Colorless oil; Rf =
0.42 (hexane/AcOEt=4/1); 1H NMR (500 MHz, CDCl3):
d=0.98 (d, J=6.6 Hz, 3H, CH3), 1.13–1.21 (m, 1H, one of
CH2), 1.35–1.39 (m, 1H, one of CH2), 1.90–2.04 (m, 2H,
CH2), 2.35 (dd, J=7.0, 2.2 Hz, 2H, CH2), 2.61 (d, J=
15.9 Hz, 1H, one of CH2), 2.89–3.02 (m, 2H, CHꢁ2), 3.21
(d, J=15.9 Hz, 1H, one of CH2), 3.36–3.37 (m, 1H, CH),
3.69 (s, 3H, CH3), 3.72 (s, 3H, CH3), 5.13 (d, J=10.1 Hz,
1H, =CH), 5.76–5.83 (m, 2H, =CHꢁ2), 9.71 (t, J=2.2 Hz,
1H, CHO); 13C NMR (125 MHz, CDCl3): d=21.0, 22.2,
23.5, 28.5, 39.1, 40.2, 42.6, 50.9, 52.4, 52.7, 62.7 (CH3, CH2,
CH and C), 126.5, 127.6, 127.9, 139.1 (=C and =CH), 170.0,
171.8 (C=O), 202.3 (CHO); IR (neat): n=2950, 1730 (CO),
1420, 1260 cmÀ1; DI-MS (EI, 70 eV): m/z (%)=320 (0), 289
886
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 879 – 888