662
C. Hammaecher et al. / Tetrahedron 61 (2005) 657–663
Table 4. Spectral data of compounds 13a–13f
Compound
IR (cmK1 a
)
GC–MSa m/z
1H NMR (CDCl3) d, J (Hz)
13C NMR (CDCl3) d, J (Hz)
13ab
2955, 1601,
1489, 1248
222 (MC), 207,
134, 105, 73
(100)
0.05 (s, 9H, SiMe3), 2.35 (d, 5JZ0.6 Hz, 3H,
SMe), 6.81 (br s, 1H, ]CH), 7.2–7.6 (m, 5H, Ph) CH), 128.5 (2!CH), 132.1 (CH), 137.6 (Cq),
140.1 (Cq)
0.1 (SiMe3), 15.0 (SMe), 126.6 (CH), 127.8 (2!
13ac
13bb
13bc
13cb
13cc
13db
13dc
13eb
0.28 (s, 9H, SiMe3), 2.19 (s, 3H, SMe), 6.93
(s, 1H, ]CH), 7.2–7.6 (m, 5H, Ph)
K0.5 (SiMe3), 17.8 (SMe), 127.2 (CH), 127.9
(2!CH), 129.3 (2!CH), 138.7 (CH), 139.7 (Cq),
140.4 (Cq)
K0.7 (SiMe3), 18.0 (SMe), 36.7 (CH2), 126.0
(CH), 128.46 (2!CH), 128.53 (2!CH), 138.0
(Cq), 140.3 (Cq), 144.6 (CH)
0.0 (SiMe3), 14.6 (SMe), 38.2 (CH2), 126.1 (CH),
128.3 (2!CH), 130.9 (CH), 135.7 (Cq), 140.8
(Cq)d
K0.8 (SiMe3), 17.9 (SMe), 32.2 (CH2), 35.1
(CH2), 125.76 (CH), 128.2 (2!CH), 128.4 (2!
CH), 137.7 (Cq), 141.6 (Cq) 145.6 (CH)
K0.2 (SiMe3), 14.5 (SMe), 34.4 (CH2), 36.6
(CH2), 125.84 (CH), 128.3 (2!CH), 132.2 (CH),
134.4 (Cq), 141.5 (Cq)d
2955, 1602,
1581, 1494,
1248
236 (MC), 221,
115, 105, 73
(100)
0.30 (s, 9H, SiMe3), 2.36 (s, 3H, SMe), 3.86
3
(d, 3JZ6.7 Hz, 2H, CH2), 6.41 (t, JZ6.7 Hz,
1H, ]CH), 7.3–7.5 (m, 5H, Ph)
0.41 (s, 9H, SiMe3), 2.29 (s, 3H, SMe), 3.70
3
(d, 3JZ7.6 Hz, 2H, CH2), 5.83 (t, JZ7.6 Hz,
1H, ]CH), 7.3–7.5 (m, 5H, Ph)
3027, 2955,
1587, 1496,
1453, 1248
250 (MC), 159
0.16 (s, 9H, SiMe3), 2.15 (s, 3H, SMe), 2.6–2.8
3
(100), 111, 105, (m, 4H, 2!CH2), 6.18 (t, JZ6.0 Hz, 1H,
73
]CH), 7.2–7.3 (m, 5H, Ph)
0.22 (s, 9H, SiMe3), 2.19 (d, 5JZ2.0 Hz, 3H,
SMe), 2.6–2.8 (m, 4H, 2!CH2), 5.66 (t,
3JZ7.3 Hz, 1H, ]CH), 7.2–7.3 (m, 5H, Ph)
0.23 (s, 9H, SiMe3), 0.89 (t, 3JZ6.6 Hz, 3H,
]CH3), 1.1–1.5 (m, 14H), 2.19 (s, 3H, SMe),
6.15 (t, 3JZ6.7 Hz, 1H, ]CH)
2924, 1587,
1465, 1248
258 (MC), 243,
159, 105, 73
(100)
K0.1 (SiMe3), 14.1 (CH3), 18.1 (CH3), 22.7
(CH2), 28.8–29.6 (4!CH2), 30.5 (CH2), 31.9
(CH2), 136.6 (Cq), 147.3 (CH)
0.17 (s, 9H, SiMe3), 0.89 (t, 3JZ6.2 Hz, 3H,
K0.8 (SiMe3), 14.7 (CH3), 20.3 (CH3), 30.4
CH3), 1.1–1.5 (m, 14H), 2.20 (s, 3H, SMe), 5.64 (CH2), 32.5 (CH2), 133.2 (Cq), 134.1 (CH)d
3
(t, JZ7.4 Hz, 1H, ]CH)
2960, 1548,
1460, 1248
216 (MC), 187,
105, 73 (100)
0.19 (s, 9H, SiMe3), 0.87 (t, 3JZ7.3 Hz, 6H, 2! 0.40 (SiMe3), 11.8 (2!CH3), 15.2 (SMe), 27.5
CH3), 1.1–1.3 (m, 4H, 2!CH2), 2.21 (s, 3H,
SMe), 2.7–2.9 (m, 1H), 5.88 (d, 3JZ9.3 Hz, 1H,
]CH)
(2!CH2), 44.6 (CH), 136.7 (Cq), 152.6 (CH)
13ec
13fb
0.25 (s, 9H, SiMe3), 0.85 (t, 3JZ7.3 Hz, 6H, 2! K0.44 (SiMe3), 11.6 (2!CH3), 18.4 (SMe), 28.1
CH3), 1.4–1.6 (m, 4H, 2!CH2), 2.19 (s, 3H,
SMe), 2.7–2.9 (m, 1H); 5.43 (d, 3JZ10.6 Hz, 1H,
]CH)
(2!CH2), 42.9 (CH), 140.3 (CH)d
2961, 1587,
1460, 1248
256 (MC), 241,
105, 73 (100)
0.16 (s, 9H, SiMe3), 0.95 (t, 3JZ7.5 Hz, 3H,
K0.8 (SiMe3), 14.4 (CH3), 18.1 (CH3), 20.5
CH3), 1.4–1.6 (m, 4H, 2!CH2), 2.0–2.1 (m, 4H, (CH2), 26.9 (CH2), 28.6 (CH2), 29.5 (CH2), 30.3
2!CH2), 2.22 (s, 3H, SMe), 2.37 (q, 3JZ6.9 Hz, (CH2), 129.0 (CH), 131.72 (CH), 136.8 (Cq),
2H, CH2), 5.3–5.4 (m, 2H, 2!]CH), 6.14
147.1 (CH)
3
(t, JZ6.9 Hz, 1H, ]CH)
13fc
0.23 (s, 9H, SiMe3), 0.95 (t, 3JZ7.5 Hz, 3H,
CH3), 1.4–1.6 (m, 4H, 2!CH2), 2.0–2.1 (m, 4H, (CH2), 27.0 (CH2), 29.4 (CH2), 29.9 (CH2), 32.4
K0.1 (SiMe3), 14.7 (CH3), 18.1 (CH3), 20.5
2!CH2), 2.1–2.3 (m, 2H, CH2), 2.22 (s, 3H,
SMe), 5.3–5.4 (m, 2H, 2!]CH), 5.60 (t,
3JZ7.7 Hz, 1H, ]CH)
(CH2), 128.9 (CH), 131.75 (CH), 133.9 (CH),
143.1 (Cq)
a IR and GC–MS spectra on the mixture of stereomers.
b Major isomer.
c Minor isomer.
d Selected data.
4.8. Preparation of compounds (16a,b) and
bis(acylsilanes) (17a,b) (Scheme 9)
(]CH), 139.0 (Cq), 139.5 (Cq), 140.3 (Cq), 140.8 (Cq); IR
(film) 2953, 2908, 1553, 1494, 1247 cmK1; GCMS (EI) m/e
(%) 366 (MC), 215, 207, 105, 73 (100).
The compounds 16a,b were obtained in 52 and 30% yields
respectively using the general procedure for the Peterson
olefination (Scheme 7) except that 2 equiv of 6, 2 equiv of
n-BuLi and 1 equiv of bis(aldehyde) were used. The
compounds 17a,b were obtained in 41 and 77% yields
respectively using the hydrolysis with acetone–hydrochloric
acid 2 M (3:2) (Schemes 8 and 9).
4.8.2. Compound 16b. Yield: 30%; Mixture of 3 stereomers
(49/20/31 determined by GC); oil; 1H NMR (CDCl3) d 0.17
(s, SiMe3), 0.23 (s, SiMe3), 1.4–1.6 (m, CH2CH2CH2), 2.19
3
3
(s, SMe), 2.24 (q, JZ7.4 Hz, ]CHCH2), 2.41 (q, JZ
3
7.4 Hz, ]CHCH2), 5.61 (t, JZ7.2 Hz, ]CH), 5.64 (t,
3
3JZ7.2 Hz, ]CH), 6.14 (t, JZ6.4 Hz, ]CH), 6.17 (t,
3JZ6.4 Hz, ]CH); Selected 13C NMR data (CDCl3) d
K0.7 (SiMe3), K0.0 (SiMe3), 14.6 (SMe), 14.7 (SMe), 18.0
(SMe), 18.1 (SMe), 28.4 (CH2), 29.6 (CH2), 30.0 (CH2),
30.2 (CH2), 32.1 (CH2), 32.2 (CH2), 133.1 (]CH), 133.3
(]CH), 137.3 (Cq), 146.2 (]CH), 146.5 (]CH); IR (film)
2955, 1640, 1587, 1438, 1248 cmK1; GCMS (EI) m/e (%)
332 (MC), 317, 197, 181, 105, 73 (100).
4.8.1. Compound 16a. Yield: 52%; Mixture of 3 stereomers
(54/21/25, determined by GC); oil; 1H NMR (CDCl3) d 0.10
(s, SiMe3), 0.29 (s, SiMe3), 2.23 (s, SMe), 2.36 (s, SMe),
6.79 (s, ]CH), 6.91 (s, ]CH), 7.13 (s, Ar sym.), 7.19 (d,
3
3JZ8.0 Hz, Ar unsym.), 7.61 (d, JZ8.0 Hz, Ar unsym.),
7.66 (s, Ar sym.); 13C NMR (CDCl3) d K0.52 (SiMe3),
K0.47 (SiMe3), 0.28 (SiMe3), 0.34 (SiMe3), 15.2 (2!
SMe), 17.8 (SMe), 17.9 (SMe), 128.1 (CH Ar), 128.2 (CH
Ar), 129.0 (CH Ar), 129.1 (CH Ar), 131.97 (]CH), 132.04
(]CH), 136.0 (Cq), 136.5 (Cq), 138.3 (]CH), 138.4
4.8.3. Compound 17a. Yield: 41%; oil; 1H NMR (CDCl3) d
0.10 (s, 18H, 2!SiMe3), 3.82 (s, 4H, 2!CH2), 7.07 (s, 4H,
C6H4); 13C NMR (CDCl3) d K2.8 (SiMe3), 55.1 (CH2),