Y. Onishi et al. / Tetrahedron 58 (2002) 8227–8235
8233
Elemental analysis: C16H17O2NS (287.37); calculated
C 66.87, H 5.96, N 4.87; found C 66.79, H 5.95, N 4.85.
10.25 Hz, 1H, 4-H), 3.07 (dd, J¼6.93, 13.85 Hz, 1H, 6-Ha),
2.87 (dd, J¼6.92, 13.85 Hz, 1H, 6-Hb), 2.47 (ddd, J¼1.49,
6.43, 14.84 Hz, 1H, 3-Ha), 1.54 (ddd, J¼7.33, 10.25,
14.84 Hz, 1H, 3-Hb), 1.52 (d, J¼6.43 Hz, 1H, OH; D2O
exchange). 13C NMR (67.9 MHz, CDCl3): d¼144.19 (s,
1-Ph), 135.90 (d, 2-C), 134.61 (d, 7-C), 127.65–127.61 (d,
2-Ph, 3-Ph), 126.23 (d, 4-Ph), 117.74 (t, 1-C), 117.35 (t,
8-C), 72.84 (d, 4-C), 55.21 (s, 5-C), 42.74 (t, 6-C), 37.69 (t,
3-C). IR (neat): n¼3563 (OH), 1639 (CvC). MS (EI,
70 eV): 278 (Mþþ1, 0.13), 237 (Mþ2allyl, 6.29), 208
(Mþ2C4H7O, 55.9), 91 (PhCHþ3 , 50.2), 77 (Phþ, 8.65).
HRMS (CI, 70 eV): calculated (C20H23O) 279.1749
(Mþþ1); found 279.1722.
4.2.2. 4-Methyl-N-(1-pentyl-but-3-enyl)-benzenesulfona-
mide (4c). Prepared by the typical procedure from
N-hexylidene-4-methyl-benzenesulfonamide (3 mmol) and
allyltrimethylsilane (6 mmol) under InCl3 (0.3 mmol) in dry
CH3NO2 (6 mL). A colorless liquid 4c (0.63 g, 79%) was
obtained, after chromatography (hexane/EtOAc, 8:2) and
distillation. Bp 1508C/1.1£1021 mm Hg. 1H NMR
(270 MHz, CDCl3): d¼7.77 (d, J¼8.31 Hz, 2H, aroma),
7.29 (d, J¼8.31 Hz, 2H, aroma), 5.66–5.51 (m, 1H, 3-H),
5.02–4.92 (m, 2H, 4-H2), 4.83 (d, J¼8.30 Hz, 1H, NH),
3.32–3.12 (m, 1H, 1-H). 2.42 (s, 3H, CH3), 2.12 (t,
J¼6.35 Hz, 2H, 2-H2), 1.45–1.12 (m, 8H, alkyl-H2), 0.81 (t,
J¼6.83 Hz, 3H, terminal-H3). 13C NMR (67.9 MHz,
CDCl3): 143.06 (s, 4-Ph), 138.18 (s, 1-Ph), 133.38 (d,
C-3), 129.44 (d, aroma-CH), 127.030(d, aroma-CH)0, 118.47
(t, C-40), 53.26 (d, C-10), 39.12 (t, C-3 ), 34.28 (t, C-10), 31.33
(t, C-3 ), 24.90 (t, C-2 or0C-40), 22.36 (t, C-20 or C-4 ), 21.40
(q, CH3), 13.83 (q, C-5 ). IR (neat): n¼3278 (NH), 1643
(CvC). MS (EI, 70 eV): 295 (Mþþ1, 0.2), 254 (Mþ2allyl,
100), 155 (Tsþ, 55.9), 91 (PhCHþ3 , 50.2). HRMS (CI,
70 eV): calculated (C16H26O2NS) 296.1606 (Mþþ1); found
296.1675. Elemental analysis: C16H25O2NS (295.44);
calculated C 65.05, H 8.53, N 4.74; found C 65.07, H
8.67, N 4.64.
4.2.5. 4-Methyl-4-phenylhepta-1,6-diene (12d). Prepared
by the typical procedure from acetophenone (3 mmol) and
allyltrimethylsilane (9 mmol) under InCl3 (0.15 mmol) and
(CH3)2ClSiOSiCl(CH3)2 (0.2 mmol) in dry CH3NO2
(3 mL). A colorless liquid 12d (0.21 g, 38%) was obtained,
after chromatography (hexane) and distillation. Bp 408C/
1.1£1021 mm Hg. 1H NMR (270 MHz, CDCl3): 7.33–7.26
(m, 4H, aroma), 7.21–7.14 (m, 1H, aroma), 5.60–5.45 (m,
2H, 2,6-H), 5.01–4.92 (m, 4H, 1,7-H2), 2.51 (dd, J¼13.67,
6.35 Hz, 1H, 3,5-Ha), 2.29 (dd, J¼13.67, 7.81 Hz, 1H, 3,5-
Hb), 1.27 (s, 3H, CH3). 13C NMR (67.9 MHz, CDCl3):
147.06 (s, 1-Ph), 135.05 (d, C-2,6), 127.99 (d, aroma-CH),
126.39 (d, aroma-CH), 125.59 (s, 4-Ph), 117.14 (t, C-1.7),
46.93 (t, C-3,5), 40.59 (s, C-4), 24.12 (q, CH3). IR (neat):
1639 (CvC). MS (CI, 70 eV): 187 (Mþþ1, 12.1), 145
(Mþ2allyl, 100), 109 (Mþ2Ph, 23). HRMS (CI, 70 eV):
calculated (C14H19) 187.1409 (Mþþ1); found 187.1472,
187.1487, 187.1481. Elemental analysis: C14H18 (186.29);
calculated C 90.26, H 9.74; found C 78.63, H 9.08.
4.2.3. 4,5-Bis(trimethylsiloxy)-3-phenyl-hexene (7). Pre-
pared by the typical procedure from 2-hydroxy-1-phenyl-
propan-1-one (2 mmol) and allyltrimethylsilane (6 mmol)
under InCl3 (0.2 mmol) and chlorotrimethylsilane
(0.4 mmol) in dry nitromethane (4 mL). A colorless liquid
7 (0.12 g, 36%) was obtained after chromatography
1
(hexane) and distillation. Bp 1158C/1.1£1021 mm Hg. H
4.2.6. 4-Methyl-4-(4-chlorophenyl)hepta-1,6-diene (12f).
Prepared by the typical procedure from p-chloroaceto-
phenone (6 mmol) and allyltrimethylsilane (9 mmol) under
InCl3 (0.3 mmol) and chlorotrimethylsilane (0.3 mmol) in
dry ClCH2CH2Cl (12 mL). A colorless liquid 12f (0.22 g,
22%) was obtained, after chromatography (hexane) and
distillation. Bp 738C/1.1£1021 mm Hg. 1H NMR
(270 MHz, CDCl3): 7.29–7.21 (m, 4H, aroma), 5.58–5.43
(m, 2H, 2,6-H), 5.00–4.94 (m, 4H, 1,7-H2), 2.47 (dd,
J¼13.67, 6.34 Hz, 1H, 3,5-Ha), 2.28 (dd, J¼13.67, 7.81 Hz,
1H, 3,5-Hb), 1.26 (s, 3H, CH3). 13C NMR (67.9 MHz,
CDCl3): 145.56 (1-Ph), 134.58 (C-2,6), 131.37 (4-Ph),
128.08 (aroma-CH), 127.93 (aroma-CH), 117.52 (C-1,7),
46.88 (C-3,5), 40.48 (C-4), 24.07 (CH3). IR (neat): 1639
(CvC). MS (EI, 70 eV): 220 (Mþ, 0.4), 179 (Mþ2allyl,
100). HRMS (EI, 70 eV): calculated (C8H17Cl) 220.1019
(Mþ); found 220.1030. Elemental analysis: C14H17Cl
(220.74); calculated C 76.18, H 7.76; found C 75.97, H 7.87.
NMR (270 MHz, CDCl3): 7.33–7.14 (m, 5H, aroma), 5.57–
5.42 (m, 1H, 2-H), 4.92–4.85 (m, 2H, 1-H), 3.94 (q,
J¼6.35 Hz, 1H, 5-H), 2.99 (dd, J¼15.13, 6.35 Hz, 1H,
3-Ha), 2.45 (dd, J¼15.13, 7.32 Hz, 1H, 3-Hb), 0.78 (d,
J¼6.35 Hz, 3H, 6-H), 0.23 (s, 9H, OSiMe3), 0.18 (s, 9H,
OSiMe3). 13C NMR (67.9 MHz, CDCl3): 145.09 (s, 1-Ph),
134.71 (d, C-2), 127.70 (d, aroma-CH), 126.11 (d, 4-Ph),
125.90 (d, aroma-CH), 116.91 (t, C-1), 83.42 (s, C-4), 74.88
(d, C-5), 42.96 (t, C-3), 17.70 (q, C-6), 2.88 (q, OSiMe3),
0.39 (q, OSiMe3). IR (neat): 1643 (CvC). MS (CI, 70 eV):
337 (Mþþ1, 2.9), 295 (Mþ2allyl, 52.1), 247
(Mþ2OSiMe3, 100). HRMS (CI, 70 eV): calculated
(C18H33O2Si2) 337.1941 (Mþþ1); found 337.2001.
Elemental analysis: C18H32O2Si2 (336.62); calculated C
64.23, H 9.58; found C 64.08, H 9.44.
4.2.4. 5,5-Diphenyl-octa-1,7-diene-4-ol (8). Prepared by
typical procedure from benzoin (2 mmol) and allyl-
trimethylsilane (6 mmol) under InCl3 (0.1 mmol) in dry
CH3NO2 (4 mL). A pale yellow liquid 8 (0.17 g, 30%) was
obtained, after chromatography (hexane/EtOAc, 19:1) and
distillation. Bp 1208C/1.1£1021 mm Hg. 1H NMR
(270 MHz, CDCl3): d¼7.34–7.16 (m, aroma, 10H), 5.87
(dddd, J¼6.43, 7.33, 10.49, 16.80 Hz, 1H, 2-H), 5.41 (dddd,
J¼6.92, 6.93, 9.89, 16.81 Hz, 1H, 7-H), 5.01 (dd, J¼0.98,
16.81 Hz, 1H, 8-Hcis), 5.01 (dd, J¼0.99, 16.80 Hz, 1H,
1-Hcis), 4.94 (dd, J¼0.99, 10.49 Hz, 1H, 1-Htrans), 4.94 (dd,
J¼0.98, 9.89 Hz, 1H, 8-Htrans), 4.43 (ddd, J¼1.49, 6.43,
Acknowledgements
This work was supported by a Grant-in Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science and Technology of the Japanese Government and
this research has been carried out at the strategic research
base ‘Handai Frontier Research Center’ supported by the
Japanese Government’s Special Coordination Fund for
Promoting Science and Technology.