T. Nakagawa et al.
Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
245
(270 MHz, CDCl3) ꢂ 1.13 (s, 3H), 1.20 (s, 3H), 3.04 (s, 6H), 3.13
(dd, J ¼ 3:5, 16.5 Hz, 1H), 3.53 (dd, J ¼ 1:9, 16.5 Hz, 1H), 3.65
(s, 3H), 3.80 (dd, J ¼ 3:8, 10.3 Hz, 1H), 6.61 (d, J ¼ 8:9 Hz, 2H),
7.14–7.22 (m, 5H), 7.82 (d, J ¼ 8:9 Hz, 2H); 13C NMR (68 MHz,
CDCl3) ꢂ 21.7, 24.7, 38.9, 40.1, 46.2, 48.1, 51.8, 110.6, 125.2,
126.6, 127.8, 129.4, 130.2, 140.4, 153.1, 177.9, 196.1; Anal.
Calcd for C22H27NO3: C, 74.76; H, 7.70; N, 3.96%. Found: C,
74.57; H, 7.68; N, 3.99%.
Dimethyl 2,2-Dimethylglutarate (16).25 Colorless oil; IR
(neat, cmꢂ1) 2993, 2954, 1736, 1443; 1H NMR (270 MHz,
CDCl3) ꢂ 1.19 (s, 6H), 1.85–1.91 (m, 2H), 2.26–2.32 (m, 2H),
3.67 (s, 6H); 13C NMR (68 MHz, CDCl3) ꢂ 25.0, 30.0, 35.1,
41.6, 51.7, 173.9, 177.7.
Methyl 2-(3-Oxocyclopentyl)propionate (17).7c,11,26 (Syn/
anti ¼ 59=41) Colorless oil; IR (neat, cmꢂ1) 2947, 1736; 1H NMR
(270 MHz, CDCl3) ꢂ 1.19 (s, 1.23H), 1.22 (s, 1.23H), 1.23 (s,
1.77H), 1.25 (s, 1.77H), 1.51–1.63 (m, 1H), 1.88–2.00 (m, 1H),
2.10–2.43 (m, 6H), 3.69 (s, 1.77H), 3.71 (s, 1.23H); 13C NMR
(68 MHz, CDCl3) Syn isomer: ꢂ 15.2, 27.2, 38.5, 40.0, 43.4,
44.37, 51.6, 175.6, 217.9, Anti isomer (detectable peak): ꢂ 15.8,
1157, 972; 1H NMR (270 MHz, CDCl3) ꢂ 1.20–1.29 (m, 6H),
1.50–1.68 (m, 1H), 1.81–2.02 (m, 1H), 2.12–2.61 (m, 6H),
2.83–2.94 (m, 2H); 13C NMR (68 MHz, CDCl3) Syn isomer: ꢂ
14.4, 16.7, 23.2, 27.8, 38.6, 40.4, 42.7, 53.5, 202.49, 217.9, Anti
isomer (detectable peak): ꢂ 15.8, 27.3, 38.4, 40.1,ꢁ 43.3, 53.6,
ꢁ
202.54, 217.9; GC (Tinj ¼ Tdet ¼ 200 C, Tcol ¼ 160 C) Syn iso-
mer: tR ¼ 18:0 min, Anti isomer: tR ¼ 19:1 min; HRMS (FAB+)
calcd for C10H17O2S [M + H]þ 201.0944, found m=z 201.0975.
S-t-Butyl 2-(3-Oxocyclohexyl)propanethioate (22).30 (Syn/
anti ¼ 80=20) The diastereomeric ratio was determined by GC
compared with the authentic sample prepared by the reported
method.29 Colorless oil; IR (neat, cmꢂ1) 2954, 1713, 1682, 957;
1H NMR (270 MHz, CDCl3) ꢂ 1.12 (d, J ¼ 6:8 Hz, 2.4H), 1.16
(d, J ¼ 7:0 Hz, 0.6H), 1.46 and 1.47 (2s, 9H), 1.38–2.48 (m,
10H); 13C NMR (68 MHz, CDCl3) Syn isomer: ꢂ 14.7, 24.9,
29.2, 29.7, 41.3, 41.7, 44.9, 48.1, 53.7, 203.3, 210.8, Anti isomer
(detectable peak): ꢂ 14.9, 24.8, 28.1, 41.1, 41.6, 45.8, 53.5, 203.1,
210.7; GC (Tinj ¼ Tdet ¼ 200 ꢁC, Tcol ¼ 160 ꢁC) Syn isomer: tR
¼
16:5 min, Anti isomer: tR ¼ 17:4 min; Anal. Calcd for
C13H22O2S: C, 64.42; H, 9.15. Found: C, 64.13; H, 9.41.
27.7, 38.6, 40.2, 42.7, 44.43, 175.5, 217.7; GC (Tinj ¼ Tdet
¼
ꢁ
ꢁ
200 C, Tcol ¼ 130 C) Syn isomer: tR ¼ 17:6 min, Anti isomer:
tR ¼ 16:6 min.
This study was supported in part by a Grant of the 21st Cen-
tury COE Program, Ministry of Education, Culture, Sports,
Science and Technology (MEXT).
The authors wish to thank Dr. Hironori Tsutsui, Mr.
Masakazu Nagasawa, and Mrs. Tomoko Shinohara, Otsuka
Pharmaceutical Company, for their kind help with IR, high
resolution mass spectrometry, and elemental analyses.
S-Ethyl (3-Oxocyclopentyl)thioacetate (18). Colorless oil;
IR (neat, cmꢂ1) 2962, 2939, 1743, 1682; 1H NMR (270 MHz,
CDCl3) ꢂ 1.26 (t, J ¼ 7:6 Hz, 3H), 1.52–1.73 (m, 1H), 1.90 (dd,
J ¼ 9:2, 18.1 Hz, 1H), 2.12–2.40 (m, 3H), 2.47 (dd, J ¼ 5:7,
17.8 Hz, 1H), 2.57–2.74 (m, 3H), 2.90 (q, J ¼ 7:6 Hz, 2H);
13C NMR (68 MHz, CDCl3) ꢂ 14.8, 23.5, 29.2, 34.1, 38.3, 44.4,
49.1, 197.7, 217.9; Anal. Calcd for C9H14O2S: C, 58.03; H,
7.58%. Found: C, 57.79; H, 7.73%.
References
2-Methyl-1,3,5-triphenylpentane-1,5-dione (19).3b,27 (Syn/
anti ¼ 26=74) Colorless oil; IR (neat, cmꢂ1) 1682, 1450, 972,
756, 702; 1H NMR (270 MHz, CDCl3) ꢂ 1.01 (d, J ¼ 6:8 Hz,
0.78H), 1.28 (d, J ¼ 6:5 Hz, 2.22H), 3.20–3.53 (m, 2H), 3.79–
4.00 (m, 2H), 7.09–7.54 (m, 11H), 7.83–7.88 (m, 3.48H), 8.05
(d, J ¼ 7:3 Hz, 0.52H); 13C NMR (68 MHz, CDCl3) Syn isomer
(detectable peak): ꢂ 16.6, 43.5, 44.3, 45.6, 126.8, 128.3, 128.8,
133.2, 136.7, 136.8, 141.4, 198.5, 203.8, Anti isomer: ꢂ 14.0,
39.7, 42.7, 45.9, 126.5, 127.9, 128.0, 128.1, 128.4, 128.5, 128.6,
132.8, 132.9, 136.6, 137.0, 142.8, 198.4, 203.2.
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2-(3-Oxo-1,3-diphenylpropyl)cyclohexanone (20).6b,28 Ma-
jor isomer: White crystals; mp 149–150 ꢁC; IR (KBr, cmꢂ1
)
2920, 1710, 1683, 1449, 747, 698, 570; 1H NMR (270 MHz,
CDCl3) ꢂ 1.18–1.33 (m, 1H), 1.57–1.77 (m, 4H), 1.96–2.05 (m,
1H), 2.34–2.55 (m, 2H), 2.68–2.77 (m, 1H), 3.17–3.27 (m, 1H),
3.45–3.53 (m, 1H), 3.68–3.77 (m, 1H), 7.13–7.28 (m, 5H),
7.38–7.54 (m, 3H), 7.89–7.92 (m, 2H); 13C NMR (68 MHz,
CDCl3) ꢂ 24.1, 28.5, 32.4, 41.1, 42.3, 44.2, 55.8, 126.6, 128.1,
128.3, 128.4, 132.8, 137.0, 142.0, 198.8, 213.7. Minor isomer:
White crystals; mp 134–135 ꢁC; IR (KBr, cmꢂ1) 2925, 1710,
5
a) E. D. Bergmann, D. Ginsburg, and R. Rappo, ‘‘Organic
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1
1687, 1449, 1248, 746, 698, 685; H NMR (270 MHz, CDCl3) ꢂ
1.14–1.21 (m, 1H), 1.48-1.64 (m, 2H), 1.83–2.02 (m, 3H), 2.13–
2.35 (m, 2H), 2.60–2.66 (m, 1H), 3.27–3.50 (m, 2H), 3.83–3.90
(m, 1H), 7.05–7.19 (m, 5H), 7.33–7.48 (m, 3H), 7.86–7.90 (m,
2H); 13C NMR (68 MHz, CDCl3) ꢂ 24.9, 27.6, 29.8, 40.2, 40.3,
42.5, 55.8, 126.3, 128.1, 128.2, 128.4, 132.8, 136.9, 142.5,
198.9, 211.7.
6
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7
a) J. Boyer, R. J. P. Corriu, R. Perz, and C. Reye, J. Orga-
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anti ¼ 59=41) The diastereomeric ratio was determined by GC
compared with an authentic sample prepared by the reported
method.29 Colorless oil; IR (neat, cmꢂ1) 2970, 1743, 1682,
8
a) V. M. Swamy and A. Sarkar, Tetrahedron Lett., 39,