M. Uemura et al. / Tetrahedron 62 (2006) 3523–3535
3533
5.17.6. (4-Buthoxyphenyl)(1,2,3,4,5-pentamethyl-2,4-
cyclopentadienyl)methanol (2f). IR (neat) 3469, 2931,
5.17.11. (4-Butoxyphenyl)(1,2,3,4,5-pentamethyl-2,4-
cyclopentadienyl)(trimethylsiloxy)methane (2f-Si). IR
(neat) 619, 750, 841, 891, 1070, 1173, 1250, 1512, 1612,
2959 cmK1; 1H NMR (CDCl3) d K0.02 (s, 9H), 0.96 (t, JZ
7.2 Hz, 3H), 1.11 (s, 3H), 1.40–1.52 (m, 8H), 1.67–1.78 (m,
5H), 1.94 (s, 3H), 3.88 (t, JZ6.6 Hz, 2H), 4.56 (s, 1H),
6.56–6.62 (m, 2H), 6.83–6.91 (m, 2H); 13C NMR (CDCl3) d
K0.02, 10.59, 10.66, 10.90, 12.67, 13.92, 18.24, 19.26,
31.42, 60.96, 67.44, 79.84, 112.03, 127.11, 133.92, 135.39,
135.41, 137.40, 139.59, 157.58. Found: C, 74.30; H, 9.83%.
Calcd for C24H38O2Si: C, 74.55; H, 9.91%.
1
1612, 1512, 1446, 1244, 1174, 1029, 821, 603 cmK1; H
NMR (C6D6) d 0.80 (t, JZ7.5 Hz, 3H), 1.22 (s, 3H), 1.20–
1.30 (m, 1H), 1.30 (dq, JZ7.5, 7.5 Hz, 2H), 1.51 (s, 3H),
1.54 (dd, JZ7.5, 7.5 Hz, 2H), 1.59 (s, 3H), 1.67 (s, 3H),
2.07 (s, 3H), 3.59 (t, JZ7.5 Hz, 2H), 4.56 (d, JZ3.0 Hz,
1H), 6.77 (d, JZ3.5 Hz, 2H), 7.15 (d, JZ3.5 Hz, 2H); 13C
NMR (C6D6) d 10.94 (C!2), 11.41, 12.24, 13.95, 18.58,
19.49, 31.64, 61.45, 67.35, 78.35, 113.18, 128.29, 134.08,
135.98, 136.07, 138.46, 139.74, 158.78. Found: C, 79.91; H,
9.68%. Calcd for C21H30: C, 80.21; H, 9.62%.
Compound 3b: IR (neat) 839, 1074 cmK1 1H NMR
;
(CDCl3) d 1.15 (d, JZ7.0 Hz, 3H), 1.61 (s, 3H), 1.72 (br
s, 3H), 1.74 (br s, 3H), 2.20–2.31 (m, 3H), 2.51 (distorted q,
1H), 5.97 (dd, JZ5.5, 10.0 Hz, 1H), 7.96–8.09 (m, 4H),
8.14–8.17 (m, 3H), 8.26–8.29 (m, 2H); 13C NMR (CDCl3) d
9.73, 12.46, 20.35, 25.07, 43.45, 50.54, 54.79, 75.93, 95.96,
122.93, 123.21, 124.71, 124.75, 124.84, 124.92, 125.09,
125.66, 126.80, 127.10, 127.51, 127.83, 130.39, 130.65,
131.30, 132.51, 135.62, 138.74. Found: C, 88.18; H, 7.21%.
Calcd for C27H26O: C, 88.48; H, 7.15%. Mp 131.2–
132.4 8C.
5.17.7. 1-{4-[(Hydroxy)(1,2,3,4,5-pentamethyl-2,4-cyclo-
pentadienyl)methyl]phenyl}-2-methyl-1-propanone (2g).
IR (neat) 3492, 2872, 1682, 1606, 1382, 1228, 981, 823,
759, 704 cmK1; 1H NMR (C6D6) d 1.06 (d, JZ7.0 Hz, 6H),
1.14 (s, 3H), 1.43 (d, JZ3.0 Hz, 1H), 1.46 (s, 3H), 1.50 (s,
3H), 1.60 (s, 3H), 2.02 (s, 3H), 3.11 (septet, JZ7.0 Hz, 1H),
4.46 (d, JZ3.0 Hz, 1H), 7.18 (d, JZ8.5 Hz, 2H), 7.81 (d,
JZ8.5 Hz, 2H); 13C NMR (C6D6) d 10.78, 10.85, 11.27,
12.39, 18.31, 19.21, 19.28, 35.26, 61.29, 78.14, 126.94,
127.10, 134.98, 136.10, 136.41, 137.72, 139.64, 147.46,
203.68. Found: C, 80.71; H, 8.94%. Calcd for C21H28O2: C,
80.73; H, 8.78%.
Compound 4b: IR (Nujol) 852, 1076 cmK1 1H NMR
;
(500 MHz, ppm, CDCl3) d 1.11 (d, JZ7.0 Hz, 3H), 1.56 (s,
3H), 1.63 (br s, 3H), 1.67–1.74 (m, 1H), 1.87 (br s, 3H), 2.24
(distorted q, 1H), 2.36 (m, 1H), 2.90 (m, 1H), 5.97 (dd, JZ
5.5, 10.5 Hz, 1H), 7.96–8.09 (m, 4H), 8.14–8.17 (m, 3H),
8.21 (d, JZ7.5 Hz, 1H), 8.29 (d, JZ9.0 Hz, 1H); 13C NMR
(CDCl3) d 9.79, 12.53, 19.63, 25.45, 44.55, 47.99, 56.03,
77.65, 96.41, 122.82, 123.11, 124.69, 124.75, 124.92,
124.95, 125.10, 125.72, 126.75, 127.06, 127.51, 127.60,
130.33, 130.67, 131.37, 134.56, 135.19, 136.51. Found: C,
88.49; H, 7.14%. Calcd for C27H26O: C, 88.48; H, 7.15%.
Mp 159.4–160.8 8C.
5.17.8. (2-Methoxyphenyl)(1,2,3,4,5-pentamethyl-2,4-
cyclopentadienyl)methanol (2h). IR (neat) 3469, 2925,
1
1600, 1587, 1490, 1400, 1240, 1033, 752, 607 cmK1; H
NMR (C6D6) d 1.30 (s, 3H), 1.57 (d, JZ1.0 Hz, 3H), 1.67
(d, JZ1.0 Hz, 3H), 1.74 (s, 3H), 1.84 (d, JZ4.5 Hz, 1H),
2.08 (s, 3H), 3.26 (s, 3H), 5.39 (d, JZ4.5 Hz, 1H), 6.47 (d,
JZ7.5 Hz, 1H), 6.85 (dd, JZ7.5, 7.5 Hz, 1H), 7.03 (dd, JZ
7.5, 7.5 Hz, 1H), 7.46 (d, JZ7.5 Hz, 1H); 13C NMR (C6D6)
d 11.04 (C!2), 11.54, 12.08, 18.82, 54.55, 61.89, 71.90,
109.88, 120.02, 128.13, 128.87, 130.65, 135.56, 135.77,
139.49, 140.40, 157.03. Found: C, 79.16; H, 9.02%. Calcd
for C18H24O2: C, 79.37; H, 8.88%.
5.17.12. 4-[(Hydroxy)(diphenyl)methyl]benzaldehyde
(7a)20 and 4-[(hydroxy)(phenyl)methyl]benzaldehyde
(7b) .21 The title compounds are found in the literature.
5.17.9. (4-Bromophenyl)(1,2,3,4,5-pentamethyl-2,4-
cyclopentadienyl)(trimethylsiloxy)methane (2a-Si). IR
(neat) 841, 889, 1076, 1250, 1377, 1458, 1655, 2924 cmK1
;
5.17.13. 4-(1-Hydroxy-1-phenyl-3-butenyl)benzaldehyde
(7c). IR (neat) 3477, 3060, 2839, 1699, 1606, 1573, 1446,
1H NMR (CDCl3) d K0.01 (s, 9H), 1.11 (s, 3H), 1.44 (br s,
3H), 1.48 (br s, 3H), 1.79 (s, 3H), 1.93 (s, 3H), 4.56 (s, 1H),
6.83–6.88 (m, 2H), 7.15–7.20 (m, 2H); 13C NMR (CDCl3) d
K0.08, 10.52, 10.64, 10.91, 12.60, 18.07, 60.74, 79.40,
120.02, 127.72, 129.08, 135.77, 136.05, 136.83, 139.29,
140.76. Found: C, 60.84; H, 7.33%. Calcd for C20H29BrOSi:
C, 61.06; H, 7.43%.
1213, 1174, 1062, 991, 825, 731, 700 cmK1 1H NMR
;
(CDCl3) d 2.69 (s, 1H), 3.07 (dd, JZ7.2, 14.1 Hz, 1H), 3.15
(dd, JZ7.2, 14.1 Hz, 1H), 5.19–5.30 (m, 2H), 5.58–5.73 (m,
1H), 7.22–7.28 (m, 2H), 7.31–7.36 (m, 2H), 7.44–7.49 (m,
2H), 7.62–7.66 (m, 2H), 7.81–7.84 (m, 2H); 13C NMR
(CDCl3) d 46.34, 76.81, 121.18, 125.88, 126.56, 127.32,
128.44, 129.68, 132.62, 134.94, 145.53, 153.28, 191.92.
Found: C, 80.69; H, 6.55%. Calcd for C17H16O2: C, 80.93;
H, 6.39%.
5.17.10. Methyl 4-[(trimethylsiloxy)(1,2,3,4,5-penta-
methyl-2,4-cyclopentadienyl)methyl]benzoate (2d-Si).
IR (neat) 619, 710, 764, 841, 1076, 1279, 1437, 1611,
1728, 1931, 2957 cmK1; 1H NMR (CDCl3) d K0.01 (s, 9H),
1.13 (s, 3H), 1.40 (br s, 3H), 1.43 (br s, 3H), 1.81 (s, 3H),
1.94 (s, 3H), 3.87 (s, 3H), 4.65 (s, 1H), 7.02–7.07 (m, 2H),
7.72–7.76 (m, 2H); 13C NMR (CDCl3) d K0.11, 10.46,
10.60, 10.94, 12.59, 18.03, 51.87, 60.83, 79.62, 125.96,
127.47, 128.16, 135.75, 136.16, 136.70, 139.30, 147.14,
167.40. Found: C, 70.97; H, 8.49%. Calcd for C22H32O3Si:
C, 70.92; H, 8.66%.
5.17.14. 4-(1-Phenylethenyl)benzaldehyde (9). IR (neat)
3028, 2829, 2734, 1697, 1604, 1566, 1211, 1168, 840, 779,
1
704 cmK1; H NMR (CDCl3) d 5.58 (d, JZ1.0 Hz, 1H),
5.59 (d, JZ1.0 Hz, 1H), 7.30–7.38 (m, 5H), 7.51 (d, JZ
8.0 Hz, 2H), 7.86 (d, JZ8.0 Hz, 2H), 10.03 (s, 1H); 13C
NMR (CDCl3) d 116.48, 128.08, 128.16, 128.35, 128.79,
129.66, 135.59, 140.53, 147.59, 149.12, 191.80. Found: C,
86.28; H, 5.81%. Calcd for C15H12O: C, 86.51; H, 5.81%.