Synthesis of a-(Phenylsulfanyl) Carbonyl Compounds
J. Chin. Chem. Soc., Vol. 55, No. 3, 2008 657
= 14.2 Hz, J2 = 7.2 Hz, 1H), 1.83 (dq, J1 = 14.2 Hz, J2 = 7.2
Hz, 1H), 3.38, (septet, J = 6.7 Hz, 1H), 7.27-7.35 (m, 5H);
13C NMR (100 MHz, CDCl3): d = 9.1, 20.3, 20.7, 21.2,
29.2, 34.2, 60.6, 128.3, 128.7, 131.4, 135.5, 211.8; HRMS-
FAB: m/z [M+H]+ calcd. for C14H21OS: 237.1313; found:
237.1311.
3H), 1.19 (s, 3H), 1.65 (s, 3H), 1.67 (s, 3H), 1.86 (d, J =
18.4 Hz, 1H), 2.17 (d, J = 18.4 Hz, 1H), 2.35 (d, J = 17.8
Hz, 1H), 2.53 (d, J = 17.8 Hz, 1H), 9.45 (s, 1H); 13C NMR
(100 MHz, CDCl3): d = 18.3, 19.0, 23.3, 25.9, 33.7, 35.3,
43.9, 56.0, 118.5, 119.8, 125.3, 195.1; MS (EI, 70 eV): m/z
191.2 [M]+.
4-Benzyl-2-methyl-4-phenylsulfanyl-3-hexanone (2f)
The typical procedure for the preparation of 2a was
followed; 1f (128 mg, 0.56 mmol) was used as starting ma-
terial. Flash chromatography (hexane-ethyl acetate 60:1)
afforded 2f as a viscous oil. Yield: 87 mg (50%).
IR (neat): 3060, 2974, 1693, 1603, 746, 692, cm-1; 1H
NMR (400 MHz, CDCl3): d = 1.04 (t, J = 7.3 Hz, 3H), 1.08
(d, J = 6.7 Hz, 3H), 1.18 (d, J = 6.7 Hz, 3H), 1.75 (q, J = 7.3
Hz, 2H), 3.02 (d, J = 14.6 Hz, 1H), 3.25 (d, J = 14.6 Hz,
1H), 3.37 (septet, J = 6.7 Hz, 1H), 7.16-7.25 (m, 5H), 7.28-
7.35 (m, 5H); 13C NMR (100 MHz, CDCl3): d = 9.1, 20.5,
21.2, 25.0, 34.6, 36.9, 65.3, 126.5, 128.0, 128.6, 128.8,
130.5, 131.5, 135.0, 137.0, 210.9; HRMS-FAB: m/z
[M+H]+ calcd. for C20H25OS: 313.1626; found: 313.1620.
(1R*,6S*)-1-Phenylsulfanyl-8,9-diemthylbicyclo[4.4.0]-
dec-8-en-2-one (2g)
2-Benzyl-2-phenylsulfanyl-5-(tert-butyl-dimethylsilanyl-
oxy)-pentanoic acid ethyl ester (2h)
The typical procedure for the preparation of 2a was
followed; 1h (138 mg, 0.37 mmol) was used as starting ma-
terial. Flash chromatography (hexane-ethyl acetate 40:1)
afforded 2h as a yellow oil. Yield: 143 mg (85%).
IR (neat): 3062, 2954, 1724, 1471, 1095, 835, 750
cm-1; 1H NMR (400 MHz, CDCl3): d = 0.02 (s, 6H), 0.88 (s,
9H), 1.17 (t, J = 7.1 Hz, 3H), 1.60-1.79 (m, 3H), 1.87-2.01
(m, 1H), 3.05 (d, J = 14.1 Hz, 1H), 3.33 (d, J = 14.1 Hz,
1H), 3.50-3.62 (m, 2H), 4.00-4.16 (m, 2H), 7.19-7.25 (m,
5H), 7.28-7.40 (m, 3H), 7.49 (broad, d, J = 7.5 Hz, 2H); 13C
NMR (100 MHz, CDCl3): d = -5.3, 14.0, 18.4, 26.0, 27.8,
29.4, 40.2, 60.0, 61.1, 63.1, 126.8, 128.1, 128.7, 129.2,
130.3, 131.2, 136.5, 136.7, 172.6; HRMS-FAB: m/z [M+H]+
calcd. for C26H39O3SiS: 459.2389; found: 459.2386.
3,4,6,6-Tetramethyl-1-phenylsulfanyl-cyclohex-3-ene-
carbaldehyde (2i)
The typical procedure for the preparation of 2a was
followed; 1g (100 mg, 0.49 mmol) was used as starting ma-
terial. Flash chromatography (hexane-ethyl acetate 40:1)
afforded 2g as a waxy solid. Yield: 45 mg (32%).
IR (neat): 2918, 2850, 1734, 1705, 1265, 739, 704
cm-1; 1H NMR (400 MHz, CDCl3): d = 1.25 (s, 3H), 1.55 (s,
3H), 1.56-1.58 (m, 3H), 1.58-1.66 (m, 1H), 1.75-2.03 (m,
2H), 2.07-2.23 (m, 1H), 2.24-2.53 (m, 3H), 3.40-3.52 (m,
1H), 7.27-7.40 (m, 5H). HRMS-FAB: m/z [M+H]+ calcd.
for C18H23OS: 287.1470; found: 287.1463.
The typical procedure for the preparation of 2a was
followed; 1i (120 mg, 0.63 mmol) was used as starting ma-
terial. Flash chromatography (hexane-ethyl acetate 40:1)
afforded 2i as a colorless oil. Yield: 50 mg (29%).
IR (neat): 3128, 3059, 2721, 1718, 1660, 1593, 1514,
1410 cm-1; 1H NMR (400 MHz, CDCl3): d = 0.97 (s, 3H),
1.10 (s, 3H), 1.56 (d, J = 19.6 Hz, 1H), 1.61 (s, 3H), 1.66 (s,
3H), 1.67 (d, J = 19.6 Hz, 1H), 1.74 (d, J = 17.6 Hz, 1H),
1.94 (d, J = 17.6 Hz, 1H), 6.96-7.53 (m, 5H), 9.79 (s, 1H);
13C NMR (100 MHz, CDCl3): d = 18.5, 19.1, 23.3, 28.7,
29.3, 32.0, 46.6, 55.7, 122.2, 124.5, 125.4, 129.1, 130.1,
137.6, 206.0; MS (EI, 70 eV): m/z 274.1 [M]+.
2-Benzyl-5-(tert-butyl-dimethyl-silanyloxy)-2-cyano-
pentanoic acid ethyl ester (1h)
IR (neat): 2243, 1741, 1471, 1388, 837 cm-1; 1H NMR
(400 MHz, CDCl3): d = 0.04 (s, 6H), 0.89 (s, 9H), 1.17 (t, J
= 7.2 Hz, 3H), 1.52-1.61 (m, 1H), 1.75-1.86 (m, 1H), 1.87-
1.95 (m, 1H), 2.04-2.13 (m, 1H), 3.07 (d, J = 13.5 Hz, 1H),
3.20 (d, J = 13.5 Hz, 1H), 3.64 (t, J = 6 Hz, 2H), 4.15 (q, J =
7.2 Hz, 2H), 7.29-7.34 (m, 5H); 13C NMR (100 MHz,
CDCl3): d = -5.4, 13.9, 18.3, 25.9, 28.7, 34.1, 43.2, 51.3,
62.1, 62.6, 119.0, 127.8, 128.5, 130.0, 134.2, 168.6; MS
(EI, 70 eV): m/z 318.1 [M – t-Bu]+.
ACKNOWLEDGEMENT
We are grateful to the National Science Council of
Republic of China and National Dong-Hwa University for
financial support.
Received November 30, 2007.
1-Formyl-3,4,6,6-tetramethyl-3-cyclohexenecarbonitrile
(1i)
REFERENCES
1. Trost, B. M. Chem. Rev. 1978, 78, 363.
2. Trost, B. M. Acc. Chem. Res. 1978, 11, 453.
IR (neat): 2968, 2733, 2663, 2241, 1728, 1454, 1373,
816, 719 cm-1; 1H NMR (400 MHz, CDCl3): d = 1.06 (s,