T. Satoh et al. / Tetrahedron 58 *2002) 4217±4224
4223
over MgSO4. The solvent was evaporated to give a residue,
which was used in the next reaction without further puri-
®cation. Toluene +2 ml) was added to the residue and the
reaction mixture was heated under re¯ux for 2.5 h. Sat. aq.
NH4Cl was added to the reaction mixture and the whole was
extracted with CHCl3. The solution was dried over MgSO4
and the solvent was evaporated. The product was puri®ed by
silica gel column chromatography to give 14 mg +85%) of
the enone 14 as a colorless oil. IR +neat) 2925, 1673 +CO),
1368, 1070, 935 cm21; 1H NMR d 1.89 +6H, s), 3.04 +4H, s),
5.80 +2H, s), 6.07 +2H, s). MS m/z +%) 166 +M1, 5), 138
+25), 125 +20), 97 +21), 69 +100), 41 +85). Calcd for
C10H14O2: M, 166.0993. Found: m/z 166.0999.
+M1, 17), 218 +62), 147 +34), 114 +100), 91 +92). Calcd for
C22H26O2: M, 322.1931. Found: m/z 322.1934.
2.1.10. 1,10-Diphenyl-3,8-di0N-piperidinyl)decane-4,7-
dione 020). To a solution of tert-BuOK +33.7 mg;
0.3 mmol) in tert-BuOH +2 ml) and THF +2 ml) at 08C
was added dropwise with stirring a solution of 16 +67 mg;
0.1 mmol) in THF. The reaction mixture was stirred for
10 min. The reaction was quenched by sat. aq. NH4Cl
and the whole was extracted with CHCl3. The solution
was dried over MgSO4 and the solvent was evaporated.
The residue +16) was heated at 1008C in piperidine for
1 h. The excess piperidine was evaporated under vacuum.
The product was puri®ed by silica gel column chromato-
graphy to give 32 mg +94%) of 20 as a colorless oil. IR
2.1.6. 2,7-Dimethyl-2,7-di0N-piperidinyl)octane-3,6-dione
015). A solution of meso-11 +45 mg; 0.1 mmol) in piper-
idine +2 ml) was heated at 1008C for 1.5 h. The excess
piperidine was evaporated under vacuum. The product
was puri®ed by silica gel column chromatography to give
32 mg +94%) of 15 as colorless crystals. Mp 105±1068C
+EtOH±H2O). IR +KBr) 2920, 2804, 1708 +CO), 1360,
1
+neat) 2933, 1713 +CO), 1454, 1115, 788 cm21; H NMR
d 1.42 +4H, m), 1.57 +8H, m), 1.89±2.04 +4H, m), 2.50
+8H, m), 2.62±2.91 +8H, m), 3.15 +2H, m), 7.16±7.29
+10H, m). MS m/z +%) 488 +M1, trace), 203 +16), 202
+100), 91 +10). Calcd for C32H44N2O2: M, 488.3402.
Found: 488.3388.
1
1199, 1044 cm21; H NMR d 1.11 +12H, s), 1.43±1.53
+4H, m), 1.57 +8H, m), 2.37 +8H, t, J4.9 Hz), 2.91 +4H,
s). MS m/z +%) 336 +M1, trace), 127 +10), 126 +100). Calcd
for C20H36O2N2: M, 336.2777. Found: m/z 336.2799. Anal.
Calcd: C, 71.38; H, 10.78; N, 8.32. Found: C, 71.48; H,
10.98; N, 8.23.
2.1.11. 0E)-1,10-Diphenyl-2,8-decadiene-4,7-dione 022).
Colorless crystals; mp 57.5±588C +AcOEt±hexane). IR
1
+KBr) 3027, 1673 +CO), 1146, 1101, 981 cm21; H NMR
d 2.87 +4H, s), 3.54 +4H, d, J6.7 Hz), 6.11 +2H, dt, J15.8,
1.5 Hz), 7.00 +2H, dt, J15.8, 6.8 Hz), 7.20±7.40 +10H, m).
MS m/z +%) 318 +M1, 45), 201 +100), 145 +91), 117 +67), 91
+71). Calcd for C22H22O2: M, 318,1618. Found: m/z
318.1609. Anal. Calcd: C, 82.99; H, 6.96. Found: C,
82.64; H, 6.58.
2.1.7. 4,7-Dichloro-1,10-diphenyl-4,7-di0p-tolylsul®nyl)-
decane-3,8-diol 016). A mixture of colorless crystals and
oil +a mixture of several diastereomers); IR +neat) 3370
1
+OH), 1494, 1454, 1081, 1032 +SO), 752 cm21; H NMR
d 1.55±3.10 +18H, m), 3.65±4.0 +2H, m), 7.0±7.7 +18H, m).
2.1.12. 3,10-Dichloro-2,11-dimethyl-3,10-di0p-tolyl-
sul®nyl)dodecane-2,11-diol 024). Colorless oil +a mixture
of two diastereomers); IR +neat) 3348 +OH), 2937, 1081,
2.1.8. 1,10-Diphenyl-3,8-di0phenylsulfenyl)octane-4,7-
dione 018). To a solution of tert-BuOK +50 mg; 0.4 mmol)
in tert-BuOH +2 ml) and THF +2 ml) at 08C was added drop-
wise with stirring a solution of 16 +67 mg; 0.1 mmol) in
THF. The mixture was stirred for 10 min, then benzenethiol
+0.03 ml; 0.3 mmol) was added to the reaction mixture.
After 20 min, the reactions were quenched by sat. aq.
NH4Cl and 5% NaOH and the whole was extracted with
CHCl3. The solution was dried over MgSO4 and the solvent
was evaporated. The product was puri®ed by silica gel
column chromatography to give 54 mg +75%) of 18 as a
1
1042 +SO), 809 cm21; H NMR d 1.04±2.25 +12H, m,
CH2), 1.40, 1.60, 2.43 +CH3), 7.32±7.35 +4H, m), 7.54±
7.67 +4H, m).
2.1.13.
2,10-Diepoxy-2,11-dimethyl-3,10-di0p-tolyl-
sul®nyl)dodecane 025). A mixture of light yellow oil and
crystals +a mixture of two diastereomers); IR +neat) 2927,
1494, 1378, 1085, 1054 +SO), 813 cm21; 1H NMR d 0.76±
0.90 +4H, m), 1.05±1.12 +2H, m), 1.36 +6H, s), 1.52±1.63
+4H, m), 1.79 +6H, s), 1.83±1.91 +2H, m), 2.42 +6H, s), 7.30
+4H, d, J7.9 Hz), 7.52±7.54 +4H, m). MS m/z +%) 341 +4),
246 +25), 223 +77), 140 +100), 123 +44), 69 +66).
colorless oil. IR +neat) 2922, 1705 +CO), 1439, 748 cm21
;
1H NMR d 1.94±2.04 +2H, m), 2.13±2.30 +2H, m), 2.70±
2.82 +6H, m), 2.93±3.02 +2H, m), 3.64 +2H, m), 7.16±7.34
+20H, m). MS m/z +%) 538 +M1, 21), 434 +14), 117 +86), 91
+100). Calcd for C34H34O2S2: M, 538.2000. Found: m/z
538.1998.
2.1.14. 2,11-Dimethyl-2,11-di0phenylsulfenyl)dodecane-
3,10-dione 026). Colorless crystals; mp 86.5±87.58C
+Hexane). IR +KBr) 2929, 1696 +CO), 1465, 1368, 1075,
1
759 cm21; H NMR d 1.36±1.39 +4H, m), 1.41 +12H, s),
2.1.9. 1,10-Diphenyldecane-4,7-dione 019). To a solution
of tributyltin hydride +0.22 ml; 0.8 mmol) and AIBN
+16 mg; 0.1 mmol) in distilled benzene +4 ml) was added
dropwise with stirring a solution of 18 +54 mg; 0.1 mmol)
in benzene. The reaction mixture was heated under re¯ux
for 10 min. The solvent was evaporated under vacuum and
the residue was puri®ed by silica gel column chromato-
graphy to give 19 +28 mg; 86%) as a low melting solid. IR
1.61±1.64 +4H, m), 2.77 +4H, t, J7.5 Hz), 7.24±7.35 +10H,
m). MS m/z +%) 442 +M1, 3), 165 +10), 151 +100). Calcd for:
C26H34O2S2: M, 442.2001. Found: m/z 422.2007. Anal.
Calcd: C, 70.55; H, 7.74; S, 14.48. Found: C, 70.80; H,
7.75; S, 14.62.
2.1.15. 2,11-Dimethyl-1,11-dodecadiene-3,10-dione 027).
Colorless oil; IR +neat) 2929, 2852, 1678 +CO), 1451,
+KBr) 2947, 1702 +CO), 1497, 1410, 1357, 1072 cm21; H
1371, 1059, 932 cm21 1H NMR d 1.33 +4H, quint,
;
1
NMR d 1.91 +4H, quint, J7.4 Hz), 2.46 +4H, t, J7.4 Hz),
J3.6 Hz), 1.61 +4H, m), 1.87 +6H, s), 2.67 +6H, t,
2.59±2.64 +8H, m), 7.15±7.30 +10H, m). MS m/z +%) 322
J7.3 Hz), 5.75 +2H, s), 5.95 +2H, s). MS m/z +%) 222