Arylsilylcarbinol Auxiliaries
127.0, 126.0, 116.4, 77.8, 73.6, 39.8, 32.8, 32.2, 24.7, 23.3, 14.4,
7.7, 2.1. HRMS (CI/NH3) m/ z calcd for C22H39OSi [M + H]+
347.2770, found 347.2777. Anal. Calcd for C22H38OSi: C, 76.23;
H, 11.05. Found: C, 76.36; H, 11.22.
hexanal to afford, after flash chromatography (5% CH2Cl2/
hexanes), 0.23 g (92%) of 20f as a pale yellow oil: IR (neat)
3077, 3028, 2931, 2859, 1641, 1486, 1247, 1047, 911, 844 cm-1
;
1H NMR (500 MHz, CDCl3) δ 7.63-7.61 (m, 2H), 7.53-7.52
(m, 2H), 7.45-7.42 (m, 2H), 7.34-7.30 (m, 1H), 7.23 (d, J )
8.1, 2H), 5.87-5.79 (m, 1H), 5.02-5.01 (m, 1H), 4.99-4.98 (m,
1H), 4.24 (s, 1H), 3.37 (quintet, J ) 5.6, 1H), 2.28-2.20 (m,
2H), 1.50-1.48 (m, 2H), 1.35-1.28 (m, 6H), 0.91 (t, J ) 7.1
3H), 0.00 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 141.8, 141.4,
138.5, 136.2, 128.9, 127.1, 127.1, 126.8, 126.7, 116.4, 77.8, 74.9,
39.5, 32.5, 32.1, 24.3, 22.9, 14.3, -3.6. HRMS (CI/NH3) m/ z
calcd for C24H33OSi [M - CH3]+ 365.2301, found 365.2297.
ter t-Bu tyldim eth yl[(1-pen tylbu t-3-en yloxy)ph en ylm eth -
yl]sila n e (20b). The general procedure above was applied to
0.16 g (0.56 mmol) of auxiliary 19b and 75 µL (0.61 mmol) of
hexanal to afford, after flash chromatography (5% CH2Cl2/
hexanes), 0.14 g (75%) of 20b as a colorless oil: IR (neat) 3070,
2930, 1463, 1246, 1045, 835 cm-1; 1H NMR (500 MHz, CDCl3)
δ 7.28-7.25 (m, 2H), 7.19-7.13 (m, 3H), 5.84 (dddd, J ) 17.4,
10.2, 7.0, 7.0, 1H), 5.01-4.97 (m, 2H), 4.41 (s, 1H), 3.32-3.27
(m, 1H), 2.23-2.13 (m, 2H), 1.57-1.52 (m, 1H), 1.45-1.38 (m,
1H), 1.31-1.17 (m, 6H), 0.91 (s, 9H), 0.88 (t, J ) 7.1, 3H),
-0.02 (s, 3H), -0.24 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
142.5, 136.2, 128.0, 127.1, 125.9, 116.3, 76.4, 72.8, 39.4, 32.4,
31.6, 27.2, 24.6, 22.9, 17.4, 14.3, -7.1, -8.5. HRMS (CI/NH3)
m/ z calcd for C22H38OSi [M]+ 346.2692, found 346.2696. Anal.
Calcd for C22H38OSi: C, 76.23; H, 11.05. Found: C, 76.02; H,
10.85.
Dim eth ylp h en yl[(1-p en tylbu t-3-en yloxy)p h en ylm eth -
yl]sila n e (20c). The general procedure above was applied to
0.18 g (0.58 mmol) of auxiliary 19c and 78 µL (0.64 mmol) of
hexanal to afford, after flash chromatography (5% CH2Cl2/
hexanes), 0.20 g (96%) of 20c as a colorless oil: IR (neat) 3071,
2931, 1641, 1599, 1451, 1428, 1247, 1115, 1046, 832 cm-1; 1H
NMR (500 MHz, CDCl3) δ 7.45-7.43 (m, 2H), 7.37-7.34 (m,
1H), 7.31-7.28 (m, 2H), 7.22-7.19 (m, 2H), 7.14-7.11 (m, 1H),
7.04-7.02 (m, 2H), 5.82-5.74 (m, 1H), 4.99-4.95 (m, 2H), 4.36
(s, 1H), 3.31 (quintet, J ) 5.6, 1H), 2.23-2.13 (m, 2H), 1.40-
1.38 (m, 2H), 1.25-1.16 (m, 6H), 0.86 (t, J ) 7.2, 3H), 0.29 (s,
3H), 0.19 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 141.9, 137.0,
136.1, 134.7, 129.2, 127.9, 127.6, 126.7, 125.8, 116.3, 77.7, 74.8,
39.4, 32.4, 31.9, 24.2, 22.8, 14.3, -5.0, -5.7. HRMS (CI/NH3)
m/ z calcd for C24H34OSi [M - H]+ 365.2301, found 365.2294.
Anal. Calcd for C24H34OSi: C, 78.63; H, 9.35. Found: C, 78.74;
H, 9.27.
Meth yld ip h en yl[(1-p en tylbu t-3-en yloxy)p h en ylm eth -
yl]sila n e (20d ). The general procedure above was applied to
0.16 g (0.43 mmol) of auxiliary 19d and 58 µL (0.47 mmol) of
hexanal to afford, after flash chromatography (10% CH2Cl2/
hexanes), 0.10 g (57%) of 20d as a colorless oil: IR (neat) 3071,
2930, 2859, 1641, 1598, 1451, 1428, 1250, 1113, 1044, 913
cm-1; 1H NMR (500 MHz, CDCl3) δ 7.60-7.56 (m, 2H), 7.50-
7.46 (m, 2H), 7.42-7.38 (m, 1H), 7.37-7.32 (m, 3H), 7.30-
7.28 (m, 2H), 7.16-7.09 (m, 3H), 7.00-6.98 (m, 2H), 5.80-
5.72 (m, 1H), 5.00-4.98 (m, 1H), 4.97-4.96 (m, 1H), 4.72 (s,
1H), 3.34 (quintet, J ) 5.6, 1H), 2.24-2.14 (m, 2H), 1.45-1.38
(m, 2H), 1.23-1.08 (m, 6H), 0.84 (t, J ) 7.2, 3H), 0.46 (s, 3H);
13C NMR (125 MHz, CDCl3) δ 141.1, 136.1, 135.9, 135.6, 135.4,
134.4, 129.5, 129.4, 127.9, 127.7, 127.6, 127.4, 126.1, 116.4,
77.6, 74.4, 39.3, 32.4, 31.8, 24.2, 22.8, 14.3, -6.2. HRMS (CI/
NH3) m/ z calcd for C29H36OSi [M]+ 428.2535, found 428.2538.
Tr im eth yl[n a p h th -2-yl(1-p en tylbu t-3-en yloxy)m eth yl]-
sila n e (20e). The general procedure above was applied to 0.14
g (0.47 mmol) of auxiliary 19e and 64 µL (0.52 mmol) of
hexanal to afford, after flash chromatography (5% CH2Cl2/
hexanes), 0.14 g (87%) of 20e as a yellow oil: IR (neat) 3058,
2931, 1457, 1248, 1048, 848 cm-1; 1H NMR (500 MHz, CDCl3)
δ 7.82-7.75 (m, 3H), 7.61 (s, 1H), 7.47-7.40 (m, 2H), 7.33 (dd,
J ) 8.4, 1.7 1H), 5.82 (dddd, J ) 17.5, 10.1, 7.0, 7.0, 1H), 5.01-
4.97 (m, 2H), 4.35 (s, 1H), 3.36 (quintet, J ) 5.6, 1H), 2.71-
2.17 (m, 2H), 1.50-1.48 (m, 2H), 1.34-1.28 (m, 6H), 0.09 (t, J
) 7.1, 3H), -0.01 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 140.5,
136.2, 133.6, 132.3, 127.8, 127.7, 127.5, 126.0, 125.6, 125.0,
124.2, 116.4, 78.0, 75.3, 39.4, 32.4, 32.1, 24.3, 22.9, 14.3, -3.6.
HRMS (CI/NH3) m/ z calcd for C23H34OSi [M]+ 354.2379, found
354.2384. Anal. Calcd for C23H34OSi: C, 77.90; H, 9.66.
Found: C, 77.63; H, 9.41.
Tr im eth yl[1-(1-p en tylbu t-3-en yloxy)h exyl]sila n e (22a ).
The general procedure above was applied to 0.18 g (0.72 mmol)
of auxiliary 21 and 98 µL (0.80 mmol) of hexanal to afford,
after flash chromatography (2% CH2Cl2/hexanes), 0.10 g (45%)
of 22a as a pale yellow oil: IR (neat) 3077, 2930, 1464, 1247,
839 cm-1 1H NMR (500 MHz, CDCl3) δ 5.88-5.80 (m, 1H),
;
5.06-5.00 (m, 2H), 3.28 (quintet, J ) 5.8, 1H), 3.05 (q, J )
6.4, 1H), 2.25-2.21 (m, 2H), 1.59-1.50 (m, 2H), 1.42-1.26 (m,
14H), 0.91-0.87 (m, 6H), 0.03 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 136.1, 116.4, 78.5, 71.2, 38.8, 34.0, 32.6, 32.4, 32.1,
27.1, 25.3, 22.9, 22.8, 14.3, 14.3, -2.4. HRMS (CI/NH3) m/ z
calcd for C18H39OSi [M + H]+ 299.2770, found 299.2765.
Tr ie t h yl[p h e n yl(1-p h e n ylb u t -3-e n yloxy)m e t h yl]si-
la n e (20g). The general procedure above was applied to 0.11
g (0.36 mmol) of auxiliary 19a and 41 µL (0.40 mmol) of
benzaldehyde to afford, after flash chromatography (5% CH2-
Cl2/hexanes), 0.12 g (98%) of 20g as a colorless oil: IR (neat)
1
3072, 2952, 1456, 1238, 1015, 845 cm-1; H NMR (500 MHz,
CDCl3) δ 7.34-7.27 (m, 5H), 7.22-7.16 (m, 3H), 7.13 (d, J )
7.3, 2H), 5.85-5.76 (m, 1H), 5.00-4.97 (m, 2H), 4.22 (dd, J )
7.8, 5.7, 1H), 4.03 (s, 1H), 2.62-2.56 (m, 1H), 2.40-2.35 (m,
1H), 0.83 (t, J ) 7.9, 9H), 0.53-0.45 (m, 6H); 13C NMR (125
MHz, CDCl3) δ 142.1, 141.9, 135.6, 128.4, 128.3, 127.8, 127.7,
126.7, 125.9, 116.8, 79.3, 72.8, 43.1, 7.5, 1.6. HRMS (CI/NH3)
m/ z calcd for C23H33OSi [M + H]+ 353.2300, found 353.2304.
Anal. Calcd for C23H32OSi: C, 78.35; H, 9.15. Found: C, 78.12;
H, 9.26.
ter t-Bu t yld im et h yl[p h en yl(1-p h en ylb u t -3-en yloxy)-
m eth yl]sila n e (20h ). The general procedure above was
applied to 0.10 g (0.35 mmol) of auxiliary 19b and 40 µL (0.38
mmol) of benzaldehyde to afford, after flash chromatography
(5% CH2Cl2/hexanes), 0.12 g (100%) of 20h as a pale yellow
oil: IR (neat) 3080, 3027, 2929, 2856, 1642, 1492, 1454, 1247,
1055, 1023, 913, 835 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.35-
7.28 (m, 5H), 7.21-7.18 (m, 3H), 7.14 (s, br, 2H), 5.85-5.77
(m, 1H), 5.03-5.01 (m, 1H), 4.99, (s, 1H), 4.22 (dd, J ) 5.8,
7.9, 1H), 4.05 (s, 1H), 2.67-2.62 (m, 1H), 2.43-2.38 (m, 1H),
0.83 (s, 9H), 0.01 (d, J ) 2.0, 3H), -0.27 (d, J ) 2.0, 3H); 13C
NMR (125 MHz, CDCl3) δ 141.6, 141.5, 135.6, 128.3, 128.3,
128.2, 127.9, 127.4, 126.0, 116.7, 78.8, 72.7, 42.5, 27.1, 17.4,
-7.1, -8.3. HRMS (CI/NH3) m/ z calcd for C22H29OSi [M -
CH3]+ 337.1987, found 337.1987. Anal. Calcd for C23H32OSi:
C, 78.35; H, 9.15. Found: C, 78.48; H, 8.99.
Dim eth ylp h en yl[p h en yl(1-p h en ylbu t-3-en yloxy)m eth -
yl]sila n e (20i). The general procedure above was applied to
0.12 g (0.40 mmol) of auxiliary 19c and 45 µL (0.44 mmol) of
benzaldehyde to afford, after flash chromatography (10% CH2-
Cl2/hexanes), 0.14 g (93%) of 20i as a pale yellow oil: IR (neat)
3069, 3026, 2961, 1642, 1600, 1492, 1428, 1247, 1115, 1058,
913, 832 cm-1 1H NMR (500 MHz, CDCl3) δ 7.45-7.39 (m,
;
3H), 7.36-7.32 (m, 2H), 7.30-7.18 (m, 6H), 7.03-7.02 (m, 4H),
5.87-5.77 (m, 1H), 5.05-5.04 (m, 1H), 5.02-5.01 (m, 1H), 4.27
(dd, J ) 7.7, 5.6, 1H), 4.11 (s, 1H), 2.62-2.55 (m, 1H), 2.41-
2.35 (m, 1H), 0.31 (s, 3H), 0.20 (s, 3H); 13C NMR (125 MHz,
CD3OD) δ 143.0, 142.0, 137.7, 136.6, 135.7, 130.4, 129.4, 129.1,
128.7, 128.7, 128.6, 128.0, 127.2, 117.2, 80.9, 75.3, 44.3, -4.7,
-5.8. HRMS (CI/NH3) m/ z calcd for C22H23OSi [M - C3H5]+
331.1518, found 331.1518. Anal. Calcd for C25H28OSi: C, 80.59;
H, 7.57. Found: C, 80.56; H, 7.68.
[Bip h en yl-4-yl(1-p en tylbu t-3-en yloxy)m eth yl]tr im eth -
ylsila n e (20f). The general procedure above was applied to
0.21 g (0.65 mmol) of auxiliary 19f and 88 µL (0.71 mmol) of
J . Org. Chem, Vol. 68, No. 26, 2003 10143