Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes: An entry to tetraorganosilicon reagents for the silicon-based cross-coupling reaction

Article abstract of DOI:10.1021/ja051281j

Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes, highly stable tetraorganosilicon reagents, are found to react with aryl and alkenyl iodides in the presence of a palladium catalyst and K₂CO₃ as a base, significantly milder conditions compared with those ever reported for the silicon-based cross-coupling reactions. The reaction tolerates a wide range of functional groups, including silyl protectors, and allows a gram-scale synthesis to recover and reuse the silicon residue. Copyright

Full text of DOI:10.1021/ja051281j

Supporting Information for:
Alkenyl- and Aryl[2-(hydroxymethyl)phenyl]dimethylsilanes: A New Entry to Tetraorganosilicon
Reagents for the Silicon-Based Cross-Coupling Reaction
Yoshiaki Nakao,*Hidekazu Imanaka, Akhila K. Sahoo, Akira Yada, and
Tamejiro Hiyama*
Department of Material Chemistry, Graduate School of Engineering,
Kyoto University, Kyoto 615-8510 Japan
General. All manipulations of oxygen- and moisture-sensitive materials were conducted
with a standard Schlenk technique under an argon atmosphere. Flush column chromatography was
performed using Merck silica gel 60 (40–63 µm), Kanto Chemical silica gel (spherical, 40–50 µm), or
aluminium oxide 90 neutral (20–63 µm). Analytical thin layer chromatography (TLC) was performed
on Merck Kieselgel 60 F254 (0.25 mm) plates. Visualization was accomplished with UV light (254
nm) and/or an aqueous alkaline KMnO4 solution followed by heating.
Apparatus. Proton and carbon nuclear magnetic resonance spectra (1H NMR and 13C NMR)
13
were recorded on a Varian Mercury 400 (1H NMR, 400 MHz; C NMR, 101 MHz) spectrometer with
solvent resonance as the internal standard (1H NMR, CHCl3 at 7.26 ppm or C6H6 at 7.15 ppm; 13C NMR,
CDCl3 at 77.0 ppm or C6D6 at 128.0 ppm). 1H NMR data are reported as follows: chemical shift,
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling
constants (Hz), and integration. Melting points were determined using a YANAKO MP-500D. Mass
spectra were obtained with a JEOL JMS-700 (EI and CI) or JEOL JMS-HX110A (FAB+) spectrometer.
Chemicals. Unless otherwise noted, commercially available reagents were used without
purification. Diethyl ether, THF, and hexane were distilled from sodium/benzophenone ketyl.
Anhydrous DMSO was purchased from Aldrich and used without further purification. N-(2-
Diphenylphosphinobenzylidene)cyclohexylamine (4) was prepared according to the reported
procedure.1

(A) Preparation of silicon reagents
Preparation of dimethyl[2-(2-tetrahydro-2H-pyranoxymethyl)phenyl]silane.
To a mixture of 2-bromophenylmethanol (34 g, 0.18 mol) and 3,4-dihydro-2H-
pyran (18 g, 0.22 mol) were added 10 drops of concentrated hydrochloric acid, and
the resulting mixture was stirred at rt overnight. The mixture was diluted with
O
O
HMe2Si
diethyl ether, neutralized with a saturated NaHCO3 aqueous solution, dried over anhydrous MgSO4, and
concentrated in vacuo to give 2-(2-tetrahydro-2H-pyranoxymethyl)bromobenzene, which was
dissolved in THF (450 mL). The solution was added a 1.6 M n-BuLi solution in hexane (124 mL,
0.20 mol) over 40 min at –78 °C, and the resulting solution was stirred for 50 min before the addition
of chlorodimethylsilane (20 g, 0.22 mol) at –78 °C. The mixture was warmed gradually at rt
overnight and quenched with H2O. After evaporation of THF, the residue was extracted with diethyl
ether, and the combined organic layers were washed with brine and dried over anhydrous MgSO4.
Distillation under vacuum gave the title compound (38 g, 83%) as a colorless oil, bp 135 °C (1.0
mmHg). 1H NMR (400 MHz, CDCl3) δ 7.54 (dd, J = 7.2, 1.4 Hz, 1H), 7.44 (dd, J = 7.5, 0.5 Hz, 1H),
7.37, (td, J = 7.5, 1.5 Hz, 1H), 7.29 (td, J = 7.3, 1.3 Hz, 1H), 4.86 (d, J = 11.9 Hz, 1H), 4.73 (t, J = 3.6
Hz, 1H), 4.59 (d, J = 11.7 Hz, 1H), 4.56–4.51 (m, 1H), 3.98–3.89 (m, 1H), 3.60–3.52 (m, 1H),
1.94–1.45 (m, 6H), 0.364 (d, J = 3.7 Hz, 3H), 0.360 (d, J = 3.7 Hz, 3H); 13C NMR (101 MHz, CDCl3)
δ 143.6, 136.5, 134.7, 129.4, 128.3, 127.0, 98.1, 69.1, 62.1, 30.6, 25.5, 19.3, –3.0, –3.1; IR (neat) 2943,
2124, 1250, 1202, 1119, 1080, 1055, 1026, 974, 885, 837, 752 cm–1; MS (EI, 70 eV) m/z (%) 250 (M+,
0.1), 164 (12), 163 (14), 150 (17), 149 (100), 85 (22); Anal. Calcd for C14H22O2Si; C, 67.15; H, 8.86.
Found: C, 67.44; H, 8.91.
Preparation of oxasilacyclopenatane 3 from dimethyl[2-(2-tetrahydro-2H-
O
pyranoxymethyl)phenyl]silane.
Dimethyl[2-(2-tetrahydro-2H-pyranoxymethyl)-
Si
Me2
phenyl]silane (75 g, 0.30 mol) was treated with p-toluenesulfonic acid monohydrate (1.1
3
g, 6.0 mmol) in MeOH (500 mL) at rt for 16 h. After evaporation of MeOH, the residue
was distilled to give 3 (41 g, 83%) as a colorless oil, bp 45 °C (2.0 mmHg). 1H NMR (400 MHz,
CDCl3) δ 7.59 (dd, J = 7.1, 0.4 Hz, 1H), 7.42–7.37 (m, 1H), 7.33–7.28, (m, 1H), 7.23 (dd, J = 7.5, 0.7
13
Hz, 1H), 5.16 (s, 2H), 0.40 (s, 6H); C NMR (101 MHz, CDCl3) δ 149.7, 135.0, 131.0, 129.5, 126.8,
121.6, 71.5, 0.6; IR (neat) 3360, 3057, 2953, 2897, 2860, 1701, 1593, 1445, 1350, 1252, 1200, 1134,
1067, 1051, 1024, 858, 829, 791, 748, 692, 652 cm–1; MS (EI, 70 eV) m/z (%) 165 (M+, 9), 164 (58),
163 (26), 151 (13), 150 (45), 149 (100), 105 (15); Anal. Calcd for C9H12OSi; C, 65.80; H, 7.36.
Found: C, 65.60; H, 7.34.
S2

Preparation of dimethyl[2-(2-acetoxymethyl)phenyl]silane (5).
To a
O
suspension of LiAlH4 (0.38 g, 10 mmol) in diethyl ether (30 mL) was added 3 (1.64
g, 10 mmol) at 0 °C, and the resulting mixture was stirred at rt for 100 min before
the addition of acetyl chloride (7.1 mL, 100 mmol) at 0 °C. Stirring was continued
at rt overnight, and the mixture was filtered through a Florisil and then a silica gel
O
HMe2Si
5
pad. The residue was purified by flash chromatography on silica gel to give 5 (1.4g, 67%) as a
colorless oil, Rf 0.30 (hexane–ethyl acetate = 20:1). 1H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 7.0 Hz,
13
1H), 7.42–7.32 (m, 3H), 5.20 (s, 2H), 4.58–4.51 (m, 1H), 2.10 (s, 3H), 0.37 (d, J = 3.8 Hz, 6H); C
NMR (101 MHz, CDCl3) δ 170.8, 140.9, 137.2, 135.0, 129.6, 129.1, 127.8, 66.6, 21.1, –3.1; IR (neat)
2959, 2127, 1742, 1437, 1379, 1362, 1236, 1130, 1080, 1026, 966, 887, 839, 756 cm–1; MS (EI, 70 eV)
m/z (%) 208 (M+, 6), 207 (37), 194 (14), 193 (81), 165 (59), 163 (24), 152 (25), 151 (98), 150 (29), 149
(100), 148 (24), 147 (27), 145 (12), 135 (27), 134 (12), 133 (55), 131 (11), 123 (14), 121 (14), 119 (13),
117 (38), 105 (20), 91 (34), 75 (46); Anal. Calcd for C11H16O2Si; C, 63.42; H, 7.74. Found: C, 63.48;
H, 7.74.
Preparation of (E)-[2-(hydroxymethyl)phenyl]dimethyl(1-octenyl)silane (1a)
HO
by platinum-catalyzed hydrosilylation. To a solution of dimethyl[2-(2-
Hex
Si
tetrahydro-2H-pyranoxymethyl)phenyl]silane (10 g, 40 mmol) and 1-ocytne (4.4
g, 40 mmol) in hexane (4 mL) were added a 10% hexane solution of t-Bu3P (80
Me2
1a
mg, 40 µmol) and a 0.01 M hexane solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
complex (4.0 mL, 40 µmol) at 0 °C. The resulting mixture was stirred at rt for 2 h, filtered through a
Celite pad, and concentrated in vacuo. The residue was dissolved in MeOH (140 mL) and treated
with p-toluenesulfonic acid monohydrate (152 mg, 0.80 mmol) at rt for 4 h. After removal of the
solvent in vacuo, the residue was purified by flash chromatography on silica gel to give the title
compound (9.0 g, 81%) as a colorless oil, Rf 0.25 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CDCl3) δ 7.55 (dd, J = 7.3, 1.3 Hz, 1H), 7.46 (dd, J = 7.5, 0.7 Hz, 1H), 7.40 (td, J = 7.5, 1.5 Hz, 1H),
7.28 (td, J = 7.3, 1.3 Hz, 1H), 6.15 (dt, J = 18.7, 6.4 Hz, 1H), 5.83 (dt, J = 18.7, 1.5 Hz, 1H), 4.74 (s,
13
2H), 2.17–2.12 (m, 2H), 1.42–1.25 (m, 8H), 0.90–0.83 (m, 3H), 0.39 (s, 6H); C NMR (101 MHz,
CDCl3) δ 149.7, 146.4, 137.1, 135.1, 130.0, 128.2, 128.0, 127.0, 65.4, 36.8, 31.7, 28.9, 28.5, 22.6, 14.1,
–1.2; IR (neat) 3329, 2957, 2926, 2855, 1614, 1466, 1435, 1248, 1126, 1078, 991, 841, 783, 746, 687
cm–1; MS (EI, 70 eV) m/z (%) 276 (M+, 0.1), 261 (32), 243 (14), 199 (12), 177 (13), 173 (11), 166 (27),
165 (66), 164 (51), 163 (44), 160 (11), 159 (42), 151 (25), 150 (30), 149 (100), 148 (27), 147 (50), 146
(16), 145 (51), 137 (12), 135 (31), 133 (14), 131 (22), 129 (18), 105 (16), 91 (18), 75 (32), 61 (39), 59
S3

(13), 55 (11); Anal. Calcd for C17H28OSi; C, 73.85; H, 10.21. Found: C, 73.86; H, 10.42.
(E)-[2-(Hydroxymethyl)phenyl]dimethyl(5-cyano-1-pentenyl)silane
HO
(1b). Following the procedure for 1a, the reaction using the silane (1.3 g,
NC
Si
Me2
5.0 mmol) and 5-hexynenitrile (0.46 g, 5.0 mmol) gave the title
compound (1.1 g, 84%) as a colorless oil, Rf 0.30 (hexane–ethyl acetate =
1b
4:1). 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 7.2 Hz, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.40 (td, J =
7.4, 1.2 Hz, 1H), 7.29 (td, J = 7.4, 1.2 Hz, 1H), 6.06 (dt, J = 18.5, 6.0 Hz, 1H), 5.95 (d, J = 18.4 Hz,
13
1H), 4.73 (s, 2H), 2.36–2.29 (m, 4H), 1.82–1.75 (m, 2H), 0.40 (s, 6H); C NMR (101 MHz, CDCl3)
δ 146.4, 145.6, 136.2, 135.0, 131.2, 129.7, 127.7, 126.9, 119.5, 65.1, 35.2, 24.0, 16.4, –1.3; IR (neat)
3443, 2953, 2249, 1618, 1433, 1250, 1124, 1078, 991, 910, 827, 733 cm–1; MS (EI, 70 eV) m/z (%) 259
(M+, 0.3), 244 (33), 242 (18), 226 (24), 165 (39), 164 (44), 163 (22), 150 (15), 149 (100), 147 (25), 145
(20), 135 (11); Anal. Calcd for C15H21NOSi; C, 69.45; H, 8.16. Found: C, 69.68; H, 8.15.
(E)-[2-(Hydroxymethyl)phenyl]dimethyl(2-phenylethenyl)silane
(1c).
HO
Following the procedure for 1a, the reaction using the silane (0.55 g, 2.2 mmol)
and phenylacetylene (0.20 g, 2.0 mmol) gave the title compound (0.45 g, 84%) as
a colorless oil, Rf 0.20 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
Ph
Si
Me2
1c
CDCl3) δ 7.62 (dd, J = 7.4, 1.3 Hz, 1H), 7.51–7.41 (m, 4H), 7.37–7.27 (m, 4H), 6.97 (d, J = 19.2 Hz,
1H), 6.67 (d, J = 19.2 Hz, 1H), 4.79 (s, 2H), 0.52 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 146.5, 145.2,
138.0, 136.4, 135.3, 130.0, 128.6, 128.3, 127.9, 127.8, 127.1, 126.5, 65.4, –1.2; IR (neat) 3444, 3055,
2955, 2359, 1605, 1572, 1495, 1447, 1435, 1248, 1198, 1124, 1076, 1028, 991, 847, 831, 812, 777, 748,
691 cm–1; MS (EI, 70 eV) m/z (%) 268 (M+, 0.5), 253 (11), 235 (15), 165 (14), 164 (29), 163 (19), 150
(15), 149 (100), 147 (13), 137 (35), 135 (10), 105 (11), 104 (25), 103 (12), 91 (24); Anal. Calcd for
C17H20OSi; C, 76.07; H, 7.51. Found: C, 75.73; H, 7.55.
(E)-[2-(Hydroxymethyl)phenyl]dimethyl(4-octen-4-yl)silane (1g). Following
OH
the procedure for 1a, the reaction using the silane (0.55 g, 2.2 mmol) and 4-octyne
Pr
(0.22 g, 2.0 mmol) gave the title compound (0.45 g, 81%) as a colorless oil, Rf
0.25 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz, CDCl3) δ 7.54 (dd, J =
7.2, 1.2 Hz, 1H), 7.47 (dd, J = 7.2, 1.2 Hz, 1H), 7.40 (td, J = 7.3, 1.4 Hz, 1H),
Pr
Si
Me2
1g
7.30–7.26 (m, 1H), 5.80 (t, J = 7.2 Hz, 1H), 4.70 (s, 2H), 2.12–2.06 (m, 4H), 1.38 (m, 2H), 1.28–1.18
(m, 2H), 0.90 (t, J = 7.4 Hz, 3H), 0.83 (t, J = 7.2 Hz, 3H), 0.40 (s, 6H); 13C NMR (101 MHz, CDCl3)
S4

δ 146.6, 142.8, 140.2, 136.7, 135.3, 129.6, 128.0, 126.9, 65.2, 32.1, 30.8, 23.4, 22.6, 14.5, 14.0, –1.2;
IR (neat) 3319, 2957, 2930, 2870, 1611, 1466, 1435, 1377, 1248, 1124, 1078, 1015, 833, 816, 770, 750,
687 cm–1; MS (EI, 70 eV) m/z (%) 276 (M+, 0.1), 261 (19), 166 (15), 165 (100), 164 (15), 163 (24), 151
(22), 150 (12), 149 (79), 148 (13), 147 (61), 145 (30), 135 (19), 91 (11), 75 (14), 61 (19), 59 (10), 55
(10); Anal. Calcd for C17H28OSi; C, 73.85; H, 10.21. Found: C, 73.67; H, 10.06.
Preparation of 1a by the platinum-catalyzed hydrosilylation of 1-octyne using 5. A 1.0
M solution of 1-octyne in hexane (0.50 mL, 0.50 mmol) was added dropwise to a mixture of 5 (104 mg,
0.50 mmol), t-Bu3P (10% hexane solution, 10 mg, 5.0 µmol), and platinum(0)-1,3-divinyl-1,1,3,3-
tetramethyldisiloxane complex (0.01 M hexane solution, 0.50 mL, 5.0 µmol) at 0 °C. The resulting
mixture was stirred at rt for 4 h, filtered through a Florisil pad, and concentrated in vacuo. The
residue was dissolved in MeOH (2.5 mL) and water (2.5 mL) and treated with K2CO3 (1.4 g, 10 mmol)
at 50 °C for 24 h. The mixture was extracted with diethyl ether, and the combined organic layers were
washed with water and brine and dried over anhydrous MgSO4; the residue was purified by flash
chromatography on silica gel to give 1a (113 mg, 82%).
Preparation of [2-(hydroxymethyl)phenyl]dimethyl(propen-1-yl)silane [1d,
HO
(Z):(E) = 94:6]. A solution of (Z)-propen-1-ylmagnesium bromide in THF (70 mL)
[prepared from (Z)-1-bromo-1-propene (6.0 g, 50 mmol) and Mg (1.71 g, 50 mmol)]2
Si
Me2
Me
(Z):(E) = 94:6
was added to a THF (20 mL) solution of 3 (5.8 g, 35 mmol) at 0 °C, and the resulting
1d
mixture was stirred at rt overnight. The mixture was diluted with diethyl ether and
filtered to remove unreacted magnesium; the filtrate was washed with a saturated NH4Cl aqueous
solution, water, and brine and dried over anhydrous MgSO4. After removal of the solvent in vacuo,
the residue was purified by flash chromatography on silica gel to give the title compound [6.8 g, 94%,
(Z):(E) = 94:6 as estimated by GC analysis] as a colorless oil, Rf 0.26 (hexane–ethyl acetate = 7:1).
1
[Spectra of (Z)-isomer] H NMR (400 MHz, CDCl3) δ 7.59 (dd, J = 7.3, 1.5 Hz, 1H), 7.47 (d, J = 7.6
Hz, 1H), 7.41 (td, J = 7.5, 1.5 Hz, 1H), 7.29 (td, J = 7.3, 1.3 Hz, 1H), 6.52 (dq, J = 13.9, 7.0 Hz, 1H),
13
5.76 (dq, J = 13.9, 1.5 Hz, 1H), 4.72 (s, 2H), 1.64 (dd, J = 6.8, 1.6 Hz, 3 H), 0.45 (s, 6H); C NMR
(101 MHz, CDCl3) δ 146.3, 145.1, 137.5, 134.7, 129.7, 129.3, 128.2, 127.0, 65.4, 19.1, –0.2; IR (neat)
3319, 3055, 2961, 2910, 1609, 1435, 1248, 1200, 1124, 1078, 1034, 826, 777, 746, 696, 658 cm–1; MS
(EI, 70 eV) m/z (%) 206 (M+, 0.1), 191 (12), 173 (29), 166 (10), 165 (62), 164 (37), 163 (18), 150 (15),
149 (100), 148 (11), 147 (39), 145 (48), 135 (16), 131 (14), 105 (11), 91 (11), 75 (43), 61 (19); Anal.
Calcd for C12H18OSi; C, 69.84; H, 8.79. Found: C, 69.82; H, 8.81.
S5

Preparation of [2-(hydroxymethyl)phenyl]dimethyl(propen-2-yl)silane (1e). To a
solution of 3 (7.5 g, 46 mmol) in THF (50 mL) was added a 0.5 M solution of 2-
propenylmagnesium bromide in THF (100 mL, 50 mmol) at 0 °C, and the resulting
mixture was stirred at rt for 9 h. The mixture was diluted with diethyl ether, washed
with a saturated NH4Cl aqueous solution, water, and brine, and dried over anhydrous
OH
Me
Si
Me2
1e
MgSO4. After removal of the solvents in vacuo, the residue was distilled under vacuum to give the
title compound (8.4 g, 89%) as a colorless oil, bp 75 °C (0.4 mmHg). 1H NMR (400 MHz, CDCl3) δ
7.55 (dd, J = 7.4, 1.2 Hz, 1H), 7.48 (ddd, J = 7.7, 1.3, 0.5 Hz, 1H), 7.42 (td, J = 7.5, 1.5 Hz, 1H), 7.30
(td, J = 7.3, 1.5 Hz, 1H), 5.71 (dq, J = 3.1, 1.6 Hz, 1H), 5.37 (dq, J = 3.1, 1.3 Hz, 1H), 4.72 (s, 2H),
13
1.92 (br s, 1H), 1.82 (dd, J = 1.6, 1.3 Hz, 3 H), 0.44 (s, 6H); C NMR (101 MHz, CDCl3) δ 147.3,
146.6, 135.4, 135.3, 129.7, 126.9, 126.6, 65.1, 22.5, –2.1; IR (neat) 3329, 2951, 1435, 1248, 1126,
1078, 1034, 924, 835, 818, 775, 754, 696, 662 cm–1; MS (EI, 70 eV) m/z (%) 206 (M+, 0.3), 191 (26),
189 (14), 173 (39), 166 (17), 165 (100), 164 (17), 163 (23), 150 (13), 149 (75), 148 (17), 147 (78), 146
(12), 145 (61), 135 (18), 131 (14), 105 (10), 75 (30); Anal. Calcd for C12H18OSi; C, 69.84; H, 8.79.
Found: C, 69.82; H, 8.56.
Preparation of [2-(hydroxymethyl)phenyl]dimethyl(1-phenylethenyl)silane (1f).
OH
To a solution of 1-phenylethenylmagnesium bromide in THF (16 mL) [prepared from
α-bromostyrene (3.7 g, 20 mmol) and Mg (0.50 g, 21 mmol)]3 was added a THF (9
Ph
Si
Me2
mL) solution of 3 (3.0 g, 19 mmol) at rt, and the resulting mixture was stirred at rt for
1f
2 h and then at 50 °C for 2 h. The mixture was diluted with diethyl ether and filtered
to remove unreacted magnesium; the filtrate was washed with a saturated NH4Cl aqueous solution,
water, and brine and dried over anhydrous MgSO4. After removal of the solvent in vacuo, the residue
was purified by flash chromatography on silica gel to give the title compound (1.5 g, 30%) as a
colorless oil, Rf 0.28 (hexane–ethyl acetate = 5:1). 1H NMR (400 MHz, CDCl3) δ 7.61 (dd, J = 7.4,
1.3 Hz, 1H), 7.48 (dd, J = 7.6, 0.8 Hz, 1H), 7.43 (td, J = 7.4, 1.3 Hz, 1H), 7.31 (td, J = 7.3, 1.5 Hz, 1H),
7.25–7.15 (m, 3H), 7.13–7.08 (m, 2H), 6.04 (d, J = 1.4 Hz, 1H), 5.71 (d, J = 1.4 Hz, 1H), 4.73 (s, 2H),
1.55 (br s, 1H), 0.48 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 152.0, 146.5, 143.6, 135.8, 135.3, 129.9,
128.8, 128.2, 128.1, 127.1, 126.72, 126.65, 65.2, –0.8; IR (neat) 3339, 3055, 2955, 1597, 1489, 1439,
1408, 1250, 1200, 1124, 1078, 1028, 934, 831, 812, 781, 754, 708, 633 cm–1; MS (EI, 70 eV) m/z (%)
268 (M+, 0.2), 253 (6), 235 (25), 209 (10), 166 (15), 165 (100), 163 (22), 149 (32), 148 (11), 147 (60),
145 (23), 137 (22), 135 (12), 104 (20); Anal. Calcd for C17H20OSi; C, 76.07; H, 7.51. Found: C,
76.31; H, 7.48.
S6

Preparation
of
[2-(hydroxymethyl)phenyl]dimethyl(2-methyl-1-
0.5 THF solution of 2-methyl-1-
HO
propenyl)silane (1h).
A
M
Me
Si
Me2
propenylmagneisum bromide (100 mL, 50 mmol) was added to a solution of 3
Me
1h
(7.5 g, 46 mmol) in THF (50 mL) at 0 °C, and the resulting mixture was stirred at
rt overnight before dilution with diethyl ether. The mixture was washed with a saturated NH4Cl
aqueous solution, water, and brine and dried over anhydrous MgSO4. After removal of the solvents in
vacuo, flash chromatography on neutral aluminum oxide (activity grade III) gave the title compound
(7.1 g, 71%) as a colorless oil, Rf 0.26 (hexane–ethyl acetate = 5:1). 1H NMR (400 MHz, C6D6) δ
7.57 (d, J = 7.3 Hz, 1H), 7.45 (d, J = 7.7 Hz, 1H), 7.22 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 7.4 Hz, 1H),
5.41 (s, 1H), 4.63 (d, J = 5.9 Hz, 2H), 1.78 (t, J = 5.9 Hz, 1H), 1.66 (s, 3H), 1.46 (s, 3H), 0.37 (s, 6H);
13C NMR (101 MHz, C6D6) δ 153.4, 147.3, 137.5, 134.9, 129.7, 128.0, 127.0, 123.8, 65.3, 29.3, 23.2,
0.0; IR (neat) 3238, 2953, 2907, 1620, 1437, 1371, 1246, 1123, 1076, 1036, 858, 833, 816, 800, 773,
745, 700, 644, 459 cm–1; MS (EI, 70 eV) m/z (%) 220 (M+, 0.04), 205 (10), 165 (28), 164 (32), 163 (17),
150 (14), 149 (100), 148 (10), 147 (25), 145 (30), 135 (10), 105 (10), 75 (27), 61 (16); Anal. Calcd for
C13H20OSi; C, 70.85; H, 9.15. Found: C, 70.83; H, 9.23.
Preparation of [2-(hydroxymethyl)phenyl]dimethyl(phenyl)silane (2a). A 1.0
OH
M solution of phenylmagnesium bromide (65 mL, 65 mmol) in THF was added
over 15 min to a solution of 3 (9.9 g, 60 mmol) in diethyl ether (250 mL) at –78 °C,
Si
Me2
and the mixture was stirred at –78 °C for 2 h and then at rt overnight. The reaction
2a
was quenched with a saturated NH4Cl aqueous solution (40 mL) at 0 °C. The
aqueous layer was extracted with diethyl ether (2 x 60 mL), and the combined organic layers were
washed with water (2 x 75 mL) and brine (50 mL) and dried over anhydrous MgSO4. After
concentration in vacuo, the residue was purified by flash chromatography on silica gel to afford 2a
(13.8 g, 95%) as a colorless solid (mp 53–54 °C), Rf 0.39 (hexane–ethyl acetate = 4:1). 1H NMR (400
MHz, CDCl3) δ 7.59 (d, J = 7.6 Hz, 1H), 7.54–7.41 (m, 4H), 7.41–7.29 (m, 4H), 4.54 (s, 2H),
1.38–1.22 (br s, 1H), 0.62 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 146.5, 139.0, 135.8, 135.5, 133.8,
130.0, 129.2, 128.1, 128.0, 127.0, 65.3, –1.1; IR (KBr) 3298, 2953, 1427, 1250, 1111, 1076, 1018, 826,
777, 739, 702, 640, 482, 419 cm–1; MS (EI, 70 eV) m/z (%) 243 (M+, 0.1), 227 (39), 211 (12), 210 (21),
209 (100), 165 (47), 164 (11), 149 (28), 147 (18), 135 (11), 105 (12); Anal. Calcd for C15H18OSi; C,
74.33; H, 7.49. Found: C, 74.18; H, 7.52.
S7

Preparation of [2-(hydroxymethyl)phenyl]dimethyl(4-fluorophenyl)silane
(2b). Following the procedure for 2a, the reaction using a 2.0 M Et2O solution
of 4-fluorophenylmagneisum bromide (17 mL, 33 mmol) and 3 (4.9 g, 30 mmol)
gave the title compound (6.8 g, 86%) as a colorless oil, Rf 0.17 (hexane–ethyl
acetate = 4:1). 1H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 7.7 Hz, 1H),
OH
F
Si
Me2
2b
7.51–7.41 (m, 4H), 7.32 (td, J = 7.0, 1.8 Hz, 1H), 7.08–7.01 (m, 2H), 4.54 (s, 2H), 1.44 (br s, 1H), 0.61
13
(s, 6H); C NMR (101 MHz, CDCl3) δ 163.7 (d, J = 248.4 Hz), 146.5, 135.8 (d, J = 7.6 Hz), 135.5,
134.4 (d, J = 3.8 Hz), 130.1, 128.0, 127.1, 115.2 (d, J = 19.9 Hz), 65.2, –0.9; IR (neat) 3331, 2955,
1587, 1499, 1261, 1250, 1231, 1163, 1103, 1078, 826, 812, 775, 756, 517 cm–1; MS (EI, 70 eV) m/z
(%) 245 (M+–Me, 87), 243 (14), 229 (14), 228 (22), 227 (100), 183 (10), 149 (24), 147 (12), 79 (11);
Anal. Calcd for C15H17FOSi; C, 69.19; H, 6.58. Found: C, 69.19; H, 6.58.
Preparation of [2-(hydroxymethyl)phenyl]dimethyl(2-methylphenyl)silane (2c).
OH
Following the procedure for 2a, the reaction using 3 (4.9 g, 30 mmol) and a 2.0 M
solution of 2-methylphenylmagnesium bromide in THF (17 mL, 33 mmol) gave the
Si
Me2
title compound (7.6 g, 99%) as a colorless oil, Rf 0.36 (hexane–ethyl acetate = 5:1).
1H NMR (400 MHz, CDCl3) δ 7.64–7.55 (m, 2H), 7.45–7.39 (m, 2H), 7.35–7.30 (m,
Me
2c
2H), 7.23 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 7.5 Hz, 1H), 4.46 (s, 2H), 2.17 (s, 3H), 1.34 (br s, 1H), 0.64
13
(s, 6H); C NMR (101 MHz, CDCl3) δ 146.3, 143.8, 137.0, 136.7, 135.0, 134.6, 130.1, 129.8, 128.3,
127.2, 125.5, 65.2, 22.8, –0.6; IR (neat) 3339, 3055, 2955, 1589, 1437, 1258, 1128, 1078, 1032, 835,
818, 773, 745, 691, 642 cm–1; MS (EI, 70 eV) m/z (%) 256 (M+, 0.03), 242 (11), 241 (51), 225 (10), 224
(21), 223 (100), 179 (11), 178 (10), 166 (10), 165 (44), 164 (16), 163 (13), 149 (57), 147 (26), 145 (10),
105 (13), 92 (14), 91 (26); Anal. Calcd for C16H20OSi; C, 74.95; H, 7.86. Found: C, 75.24; H, 7.94.
Preparation of [2-(hydroxymethyl)phenyl]dimethyl(2-thienyl)silane (2d).
A
OH
solution of 2-thienylmagnesium bromide in THF (23 mL) [prepared from 2-
bromothiopene (5.4 g, 33 mmol) and Mg (0.82 g, 34 mmol)]4 was added to 3 (4.9 g,
30 mmol) in THF (10 mL) at 0 °C, and the resulting mixture was stirred at rt for 22
h. The mixture was diluted with diethyl ether, washed with a saturated NH4Cl
S
Si
Me2
2d
aqueous solution, water, and brine, and dried over anhydrous MgSO4. After removal of the solvent in
vacuo, flash chromatography on silica gel gave the title compound (5.9 g, 79%) as a colorless oil, Rf
0.21 (hexane–ethyl acetate = 5:1). 1H NMR (400 MHz, CDCl3) δ 7.64 (dd, J = 4.6, 0.9 Hz, 1H), 7.57
(dd, J = 7.4, 0.7 Hz, 1H), 7.50–7.41 (m, 2H), 7.34–7.28 (m, 2H), 7.20 (dd, J = 4.6, 3.4 Hz, 1H), 4.64 (s,
S8

2H), 1.47 (s, 1H), 0.68 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 146.5, 138.5, 135.6, 135.3, 131.3, 130.2,
128.4, 128.2, 127.1, 65.3, 0.2; IR (neat) 3337, 2955, 1435, 1406, 1252, 1213, 1126, 1080, 991, 833,
812, 777, 754, 710, 654 cm–1; MS (EI, 70 eV) m/z (%) 233 (M+–Me, 42), 231 (15), 217 (14), 216 (19),
215 (100), 164 (19), 163 (12), 150 (10), 149 (73); Anal. Calcd for C13H16OSSi; C, 62.85; H, 6.49.
Found: C, 62.96; H, 6.49.
(B) Cross-coupling reaction
Cross-coupling of 1a–1h with aryl iodides. A general procedure. To a mixture of K2CO3
(304 mg, 2.2 mmol), tri(2-furyl)phosphine (4.6 mg, 20 µmol), and PdCl2 (1.8 mg, 10 µmol) in DMSO
(2.5 mL) were added an alkenylsilane (1.1 mmol) and an aryl iodide (1.0 mmol) sequentially, and the
resulting mixture was stirred at 35 °C. After the time specified in Table 1, the mixture was diluted
with diethyl ether, washed with water and brine, and dried over anhydrous MgSO4. Concentration in
vacuo followed by flash chromatography on silica gel afforded the corresponding coupling product in a
yield listed in Table 1.
(E)-1-(4-Cyanophenyl)-1-octene (entry 1).
(hexane–ethyl acetate = 20:1). 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.4
A colorless oil, Rf 0.31
Hex
CN
Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 6.38–6.35 (m, 2H), 2.24–2.20 (m, 2H),
1.50–1.42 (m, 2H), 1.40–1.25 (m, 6H), 0.92–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 142.4, 135.5,
132.2, 128.3, 126.3, 119.1, 109.8, 33.1, 31.6, 28.9, 28.8, 22.5, 14.0; IR (neat) 2955, 2928, 2855, 2226,
1649, 1605, 1502, 1466, 1412, 1175, 966, 856, 733, 552 cm–1; MS (EI, 70 eV) m/z (%) 213 (M+, 18),
143 (11), 142 (34), 130 (19), 129 (100), 116 (14), 115 (11); Anal. Calcd for C15H19N; C, 84.46; H, 8.98.
Found: C, 84.37; H, 8.96.
(E)-1-(4-Ethoxycarbonylphenyl)-1-octene (entry 2). A colorless oil, Rf
0.40 (hexane–ethyl acetate = 20:1). 1H NMR (400 MHz, CDCl3) δ 7.96 (d,
Hex
CO2Et
J = 7.0 Hz, 2H), 7.38 (d, J = 7.0 Hz, 2H), 6.45–6.32 (m, 2H), 4.37 (q, J =
13
7.2 Hz, 2H), 2.23 (q, J = 7.2 Hz, 2H), 1.53–1.28 (m, 11H), 0.94–0.86 (m, 3H); C NMR (101 MHz,
CDCl3) δ 166.5, 142.4, 134.2, 129.8, 129.0, 128.5, 125.7, 60.8, 33.2, 31.7, 29.1, 28.9, 22.6, 14.3, 14.1;
IR (neat) 2957, 2928, 2855, 1715, 1607, 1466, 1412, 1366, 1275, 1177, 1107, 1020, 968, 957, 864, 762,
696 cm–1; MS (EI, 70 eV) m/z (%) 261 (M++1, 14), 260 (M+, 76), 215 (37), 177 (16), 176 (100), 161
(11), 148 (45), 145 (23), 132 (10), 131 (55), 129 (16), 128 (13), 118 (10), 117 (86), 116 (23), 115 (49),
91 (18); Anal. Calcd for C17H24O2; C, 78.42; H, 9.29. Found: C, 78.45; H, 9.41.
S9

(E)-1-(4-Acetylphenyl)-1-octene (entry 3).
A colorless oil, Rf 0.30
Hex
(hexane–ethyl acetate = 20:1). 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J =
8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 6.43–6.33 (m, 2H), 2.57 (s, 3H), 2.23 (q,
J = 6.4 Hz, 2H), 1.52–1.42 (m, 2H), 1.40–1.25 (m, 6H), 0.92–0.86 (m, 3H);
O
13C NMR (101 MHz, CDCl3) δ 197.5, 142.6, 135.3, 134.5, 128.8, 128.7, 125.8, 33.1, 31.7, 29.1, 28.9,
26.5, 22.6, 14.0; IR (neat) 2957, 2926, 2855, 1682, 1603, 1410, 1358, 1267, 1180, 966, 592 cm–1; MS
(EI, 70 eV) m/z (%) 231 (M++1, 12), 230 (M+, 73), 216 (11), 215 (72), 148 (10), 147 (15), 146 (56), 145
(11), 134 (11), 131 (100), 128 (11), 117 (19), 116 (12), 115 (36); Anal. Calcd for C16H22O; C, 83.43; H,
9.63. Found: C, 83.72; H, 9.74.
(E)-1-(4-Formylphenyl)-1-octene (entry 4). A colorless oil, Rf 0.30
(hexane–ethyl acetate = 30:1). 1H NMR (400 MHz, CDCl3) δ 9.96 (s, 1H),
Hex
H
7.80 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.64–6.42 (m, 2H),
O
2.28–2.22 (m, 2H), 1.53–1.44 (m, 2H), 1.40–1.25 (m, 6H), 0.92–0.86 (m,
13
3H); C NMR (101 MHz, CDCl3) δ 191.7, 144.1, 135.4, 134.8, 130.1, 128.9, 126.3, 33.2, 31.7, 29.0,
28.9, 22.6, 14.1; IR (neat) 2955, 2926, 2855, 1697, 1603, 1568, 1304, 1213, 1167, 966, 851, 802 cm–1;
MS (EI, 70 eV) m/z (%) 216 (M+, 43), 133 (14), 132 (100), 131 (39), 117 (62), 116 (11), 115 (29), 91
(19); Anal. Calcd for C15H20O; C, 83.28; H, 9.32. Found: C, 83.40; H, 9.37.
(E)-1-(4-Nitrophenyl)-1-octene (entry 5).
A colorless oil, Rf 0.17
Hex
(hexane–ethyl acetate = 30:1). 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J =
NO2
8.8 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H), 6.46–6.42 (m, 2H), 2.30–2.20 (m, 2H),
1.54–1.42 (m, 2H), 1.40–1.24 (m, 6H), 0.93–0.87 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 146.3, 144.4,
136.7, 128.0, 126.3, 123.9, 33.2, 31.6, 28.91, 28.87, 22.6, 14.0; IR (neat) 2955, 2928, 2855, 1649, 1597,
1518, 1466, 1342, 1109, 968, 955, 860, 824, 745, 689 cm–1; MS (EI, 70 eV) m/z (%) 234 (M++1, 11),
233 (M+, 67), 151 (12), 150 (40), 149 (100), 137 (29), 129 (13), 128 (17), 119 (22), 117 (19), 116 (79),
+
115 (70), 103 (13), 91 (11), 55 (11); HRMS (FAB+) Calcd for C14H20NO2: [M+H] , 234.1494.
Found: m/z 234.1497.
(E)-1-(4-Chlorophenyl)-1-octene (entry 6). A colorless oil, Rf 0.60 (hexane).
1H NMR (400 MHz, CDCl3) δ 7.26 (s, 4H), 6.33 (dt, J = 15.5, 1.2 Hz, 1H), 6.21
Hex
Cl
(dt, J = 15.5, 6.8 Hz, 1H), 2.20 (q, J = 6.8 Hz, 2H), 1.52–1.42 (m, 2H),
13
1.40–1.23 (m, 6H), 0.94–0.88 (m, 3H); C NMR (101 MHz, CDCl3) δ 136.4, 132.2, 132.0, 128.54,
S10

128.49, 127.1, 33.0, 31.7, 29.2, 28.9, 22.6, 14.1; IR (neat) 2957, 2926, 2855, 1709, 1491, 1466, 1404,
1092, 1013, 964, 845, 820, 802, 735 cm–1; MS (EI, 70 eV) m/z (%) 224 (M++2, 15), 222 (M+, 44), 153
(29), 152 (12), 151 (88), 140 (31), 139 (10), 138 (100), 129 (10), 125 (17), 117 (11), 116 (36), 115
+
(46) ; HRMS (EI, 70 eV) Calcd for C14H19Cl: M , 222.1175. Found: m/z 222.1172.
(E)-1-(4-Methoxyphenyl)-1-octene (entry 7). A colorless oil, Rf 0.36
(hexane–ethyl acetate = 50:1). 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J =
Hex
OMe
8.7 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 6.33 (d, J = 15.7 Hz, 1H), 6.09 (dt, J =
15.7, 7.0 Hz, 1H), 3.81 (s, 3H), 2.19 (q, J = 7.5 Hz, 2H), 1.50–1.42 (m, 2H), 1.40–1.26 (m, 6H),
0.93–0.88 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 158.6, 130.8, 129.1, 129.0, 126.9, 113.9, 55.2, 33.0,
31.8, 29.5, 28.9, 22.6, 14.1; IR (neat) 2955, 2926, 2855, 1609, 1510, 1466, 1248, 1175, 1038, 964, 841
cm–1; MS (EI, 70 eV) m/z (%) 218 (M+, 39), 148 (12), 147 (100), 134 (14), 121 (15), 91 (10); Anal.
Calcd for C15H22O; C, 82.52; H, 10.16. Found: C, 82.52; H, 9.98.
(E)-1-[3-(tert-Butyldimethylsiloxymethyl)phenyl]-1-octene
Hex
OSiMe2t-Bu
(entry 8). A colorless oil, Rf 0.35 (hexane–ethyl acetate = 50:1).
1H NMR (400 MHz, CDCl3) δ 7.30 (s, 1H), 7.25–7.13 (m, 3H), 6.37
(d, J = 15.7 Hz, 1H), 6.22 (dt, J = 15.7, 6.9 Hz, 1H), 4.72 (s, 2H), 2.20 (q, J = 7.7 Hz, 2H), 1.50–1.42
(m, 2H), 1.38–1.26 (m, 6H), 0.95 (s, 9H), 0.39 (t, J = 6.9 Hz, 3H), 0.10 (s, 6H); 13C NMR (101 MHz,
CDCl3) δ 141.5, 137.8, 131.2, 129.7, 128.3, 124.49, 124.47, 123.5, 64.9, 33.0, 31.7, 29.3, 28.9, 26.0,
22.6, 18.4, 14.1, –5.2; IR (neat) 2955, 2928, 2856, 1462, 1256, 1105, 1080, 962, 837, 777 cm–1; MS (EI,
70 eV) m/z (%) 332 (M+, 2), 276 (27), 275 (100), 245 (16), 201 (34); Anal. Calcd for C21H36OSi; C,
75.84; H, 10.91. Found: C, 75.97; H, 11.13.
(E)-1-[3-(Hydroxymethyl)phenyl]-1-octene (entry 9). A colorless oil, Rf
0.30 (hexane–ethyl acetate = 5:1). 1H NMR (400 MHz, CDCl3) δ 7.36 (s,
Hex
OH
1H), 7.32–7.27 (m, 2H), 7.21–7.18 (m, 1H), 6.38 (d, J = 15.6 Hz, 1H), 6.26
(dt, J = 16.0, 6.8 Hz, 1H), 4.68 (s, 2H), 2.21 (q, J = 7.2 Hz, 2H), 1.51–1.42 (m, 2H), 1.40–1.26 (m, 6H),
13
0.93–0.87 (m, 3H); C NMR (101 MHz, CDCl3) δ 141.0, 138.3, 131.7, 129.4, 128.7, 125.35, 125.32,
124.4, 65.4, 33.0, 31.7, 29.3, 28.9, 22.6, 14.1; IR (neat) 3329, 2955, 2926, 2855, 1466, 1433, 1020, 962,
775, 733, 696 cm–1; MS (EI, 70 eV) m/z (%) 218 (M+, 36), 134 (42), 132 (16), 131 (16), 129 (24), 128
(12), 118 (14), 117 (100), 115 (22), 105 (10), 91 (20); Anal. Calcd for C15H22O; C, 82.52; H, 10.16.
Found: C, 82.63; H, 10.40.
S11

(E)-1-(2-Methylphenyl)-1-octene (entry 10). A colorless oil, Rf 0.71 (hexane).
1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.2 Hz, 1H), 7.19–7.10 (m, 3H), 6.57 (d,
J = 15.6 Hz, 1H), 6.10 (dt, J = 15.6, 6.8 Hz, 1H), 2.34 (s, 3H), 2.23 (q, J = 7.2 Hz,
Hex
Me
2H), 1.54–1.42 (m, 2H), 1.40–1.26 (m, 6H), 0.92–0.88 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 137.1,
134.8, 132.6, 130.1, 127.5, 126.7, 126.0, 125.4, 33.3, 31.7, 29.4, 28.9, 22.6, 19.8, 14.1; IR (neat) 3020,
2957, 2926, 2855, 1485, 1460, 1377, 962, 745 cm–1; MS (EI, 70 eV) m/z (%) 202 (M+, 42), 132 (13),
131 (100), 129 (12), 118 (51), 117 (18), 116 (17), 115 (18), 105 (16), 91 (15); Anal. Calcd for C15H22; C,
89.04; H, 10.96. Found: C, 88.97; H, 11.18.
(E)-1-(1-Naphthyl)-1-octene (entry 11). A colorless oil, Rf 0.50 (hexane).
Hex
1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 7.6 Hz, 1H), 7.84 (d, J = 7.2 Hz, 1H),
7.74 (d, J = 8.0 Hz, 1H), 7.58–7.40 (m, 4H), 7.11 (d, J = 15.2 Hz, 1H), 6.24 (dt,
J = 16.0, 7.2 Hz, 1H), 2.33 (q, J = 7.6 Hz, 2H), 1.60–1.52 (m, 2H), 1.46–1.32 (m,
6H), 0.94–0.88 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 135.8, 134.6, 133.6, 131.1, 128.4, 127.1, 126.8,
125.74, 125.65, 125.58, 124.0, 123.5, 33.5, 31.8, 29.4, 29.0, 22.7, 14.1; IR (neat) 3059, 3044, 2955,
2926, 2855, 1591, 1508, 1466, 1394, 964, 775, 727 cm–1; MS (EI, 70 eV) m/z (%) 238 (M+, 44), 168
(17), 167 (100), 166 (15), 165 (35), 154 (21), 153 (24), 152 (22), 141 (13); Anal. Calcd for C18H22; C,
90.70; H, 9.30. Found: C, 90.61; H, 9.32.
(E)-1-(3-Pyridyl)-1-octene (entry 12). A colorless oil, Rf 0.35 (hexane–ethyl
acetate = 5:1). 1H NMR (400 MHz, CDCl3) δ 8.56 (br s, 1H), 8.42 (br d, J = 3.7
Hex
N
Hz, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.22 (dd, J = 7.8, 4.8 Hz, 1H), 6.38–6.26 (m, 2H),
13
2.26–2.20 (m, 2H), 1.52–1.43 (m, 2H), 1.40–1.26 (m, 6H), 0.92–0.86 (m, 3H); C NMR (101 MHz,
CDCl3) δ 147.8, 147.7, 133.8, 133.5, 132.5, 126.1, 123.4, 33.1, 31.7, 29.1, 28.9, 22.6, 14.1; IR (neat)
3024, 2955, 2926, 2855, 2359, 2341, 1653, 1568, 1466, 1414, 1022, 964, 708 cm–1; MS (EI, 70 eV) m/z
(%) 189 (M+, 46), 146 (10), 132 (10), 130 (10), 119 (14), 118 (87), 117 (37), 106 (27), 105 (100), 93
(14), 91 (15); Anal. Calcd for C13H19N; C, 82.48; H, 10.12. Found: C, 82.20; H, 10.06.
(E)-1-(2-Thienyl)-1-octene (entry 13). A colorless oil, Rf 0.70 (hexane). 1H
Hex
S
NMR (400 MHz, CDCl3) δ 7.08 (d, J = 5.2 Hz, 1H), 6.95–6.91 (m, 1H), 6.86 (d, J =
3.2 Hz, 1H), 6.50 (d, J = 15.6 Hz, 1H), 6.07 (dt, J = 15.6, 6.8 Hz, 1H), 2.17 (q, J =
7.2 Hz, 2H), 1.52–1.41 (m, 2H), 1.40–1.24 (m, 6H), 0.94–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3)
δ 131.3, 127.2, 124.1, 123.0, 122.9, 108.2, 32.9, 31.7, 29.2, 28.9, 22.6, 14.1; IR (neat) 2955, 2926,
S12

2855, 1724, 1686, 1676, 1466, 1437, 1420, 1377, 1211, 1042, 953, 853, 723, 692 cm–1; MS (EI, 70 eV)
m/z (%) 194 (M+, 41), 147 (10), 124 (12), 123 (100), 110 (46), 97 (14), 73 (18); HRMS (EI, 70 eV)
+
Calcd for C12H18S: M , 194.1129. Found: m/z 194.1126.
(E)-6-(4-Ethoxycarbonylphenyl)-5-hexenenitrile (entry 14).
colorless oil, Rf 0.30 (hexane–ethyl acetate = 5:1). 1H NMR (400
A
NC
CO2Et
MHz, CDCl3) δ 7.98 (d, J = 6.4 Hz, 2H), 7.39 (d, J = 6.8 Hz, 2H),
6.50 (d, J = 16.0 Hz, 1H), 6.31–6.22 (m, 1H), 4.36 (q, J = 7.2 Hz, 2H), 2.44–2.38 (m, 4H), 1.86 (m,
4H), 1.39 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 141.4, 131.2, 130.4, 129.9, 129.1,
125.9, 119.4, 60.9, 31.7, 24.8, 16.5, 14.3; IR (neat) 2984, 2937, 2907, 2243, 1711, 1607, 1458, 1437,
1414, 1366, 1271, 1180, 1126, 1109, 1092, 1024, 968, 955, 768, 750, 694 cm–1; MS (EI, 70 eV) m/z
(%) 244 (M++1, 14), 243 (M+, 81), 199 (15), 198 (100), 197 (16), 196 (19), 170 (12), 157 (14), 145 (15),
+
130 (14), 129 (43), 128 (22), 117 (57), 116 (16), 115 (40); HRMS (EI, 70 eV) Calcd for C15H17NO2: M ,
243.1259. Found: m/z 243.1259.
(E)-4-Ethoxycarbonylstilbene (entry 15).
A colorless solid (mp
Ph
106.0–106.5 °C), Rf 0.30 (hexane–ethyl acetate = 20:1). 1H NMR (400
CO2Et
MHz, CDCl3) δ 8.03 (d, J = 8.4 Hz, 2H), 7.58–7.52 (m, 4H), 7.41–7.36 (m,
2H), 7.32–7.27 (m, 1H), 7.22 (d, J = 16.4 Hz, 1H), 7.13 (d, J = 16.4 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H),
1.41 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 141.7, 136.7, 131.1, 130.0, 129.2, 128.8,
128.2, 127.6, 126.8, 126.3, 60.9, 14.4; IR (KBr) 2976, 1705, 1607, 1367, 1283, 1180, 1130, 1109, 1024,
976, 770, 696, 527 cm–1; MS (EI, 70 eV) m/z (%) 253 (M++1, 20), 252 (M+, 100), 208 (12), 207 (65),
180 (10), 179 (54), 178 (57); Anal. Calcd for C17H16O2; C, 80.93; H, 6.39. Found: C, 81.18; H, 6.27.
Ethyl 4-(propen-1-yl)benzoate [(Z):(E) = 94:6] (entry 16). A colorless oil, Rf
0.33 (hexane–ethyl acetate = 20:1). [Spectra of (Z)-isomer] 1H NMR (400
Me
CO2Et
MHz, CDCl3) δ 8.01 (dd, J = 8.4 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 6.46 (dd, J =
(Z):(E) = 94:6
11.8, 1.8 Hz, 1H), 5.90 (dq, J = 11.8, 7.2 Hz, 1H), 4.38 (q, J = 7.2 Hz, 2H), 1.91
(dd, J = 7.2, 1.8 Hz, 3H), 1.40 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.5, 142.2, 129.4,
129.1, 129.0, 128.7, 128.3, 60.8, 14.8, 14.3; IR (neat) 2980, 1715, 1609, 1367, 1310, 1277, 1178, 1105,
1020, 866, 773, 733, 721, 700 cm–1; MS (EI, 70 eV) m/z (%) 190 (M+, 50), 162 (12), 146 (13), 145
(100), 117 (20), 115 (25), 91 (10); Anal. Calcd for C12H14O2; C, 75.76; H, 7.42. Found: C, 75.90; H,
7.44.
S13

Ethyl 4-(propen-2-yl)benzoate (entry 17).
A colorless oil, Rf 0.40
Me
(hexane–ethyl acetate = 10:1). 1H NMR (400 MHz, CDCl3) δ 8.00 (dd, J = 8.0
Hz, 2H), 7.52 (d, J = 8.2 Hz, 2H), 5.47 (dq, J = 1.3, 0.7 Hz, 1H), 5.19 (qd, J =
1.5, 1.3 Hz, 1H), 4.38 (q, J = 7.1 Hz, 2H), 2.17 (dd, J = 1.5, 0.7 Hz, 3H), 1.40 (t,
CO2Et
J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.7, 145.8, 142.7, 129.8, 129.5, 125.6, 114.7, 61.1,
21.9, 14.6; IR (neat) 2980, 2359, 2341, 1715, 1609, 1367, 1275, 1184, 1123, 1103, 1020, 899, 860, 783,
719 cm–1; MS (EI, 70 eV) m/z (%) 190 (M+, 42), 162 (19), 146 (13), 145 (100), 115 (20); HRMS
+
(FAB+) Calcd for C12H14O2: M , 190.0994. Found: m/z 190.0993.
1-(4-Ethoxycarbonylphenyl)-1-phenylethene (entry 18). A colorless solid
(mp 46.7–47.3 °C), Rf 0.33 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CDCl3) δ 8.02 (d, J = 8.6 Hz, 2H), 7.41 (d, J = 8.6 Hz, 2H), 7.36–7.30 (m, 5H),
5.55 (d, J = 1.1 Hz, 1H), 5.54 (d, J = 1.1 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.41
CO2Et
13
(t, J = 7.1 Hz, 3H); C NMR (101 MHz, CDCl3) δ 164.4, 149.3, 145.9, 140.8,
129.7, 129.5, 128.3, 128.2, 128.0, 115.8, 60.9, 14.3; IR (KBr) 1717, 1279, 1105, 775, 702 cm–1; MS (EI,
70 eV) m/z (%) 253 (M++1, 18), 252 (M+, 97), 224 (14), 208 (18), 207 (100), 179 (44), 178 (68), 177
(11), 176 (11); Anal. Calcd for C17H16O2; C, 80.93; H, 6.39. Found: C, 81.01; H, 6.47.
1-(4-Methoxyphenyl)-1-phenylethene (entry 19).
A colorless solid (mp
75.3–76.8 °C), Rf 0.39 (hexane–ethyl acetate = 15:1). 1H NMR (400 MHz,
CDCl3) δ 7.38–7.31 (m, 5H), 7.28 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H),
13
5.41 (d, J = 1.4 Hz, 1H), 5.36 (d, J = 1.4 Hz, 1H), 3.83 (s, 3H); C NMR (101
OMe
MHz, CDCl3) δ 159.6, 149.7, 142.0, 134.2, 129.6, 128.6, 128.4, 127.9, 113.7,
113.2, 55.5; IR (KBr) 3005, 2951, 2835, 1908, 1811, 1605, 1572, 1508, 1491, 1456, 1441, 1290, 1250,
1180, 1028, 901, 843, 785, 708, 581, 552 cm–1; MS (EI, 70 eV) m/z (%) 253 (M++1, 18), 252 (M+, 97),
224 (14), 208 (18), 207 (100), 179 (44), 178 (68), 177 (11), 176 (11); Anal. Calcd for C15H14O; C,
85.68; H, 6.71. Found: C, 85.67; H, 6.73.
(E)-4-(4-Ethoxycarbonylphenyl)-4-octene (entry 20). A colorless oil, Rf
0.40 (hexane–ethyl acetate = 30:1). 1H NMR (400 MHz, CDCl3) δ 7.97 (d,
J = 8.6 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H), 5.76 (t, J = 7.3 Hz, 1H), 4.37 (q, J
CO2Et
= 7.1 Hz, 2H), 2.49 (t, J = 7.5 Hz, 2H), 2.19 (q, J = 7.3 Hz, 2H), 1.53–1.42
13
(m, 2H), 1.41–1.32 (m, 5H), 0.97 (t, J = 7.3 Hz, 3H), 0.88 (t, J = 7.3 Hz, 3H); C NMR (101 MHz,
S14

CDCl3) δ 166.6, 148.0, 139.4, 131.1, 129.5, 128.4, 126.2, 60.8, 31.4, 30.7, 22.9, 21.8, 14.4, 14.0, 13.9;
IR (neat) 2959, 2932, 2872, 1720, 1607, 1462, 1408, 1366, 1273, 1180, 1107, 1020, 858, 772, 706
cm–1; MS (EI, 70 eV) m/z (%) 261 (M++1, 15), 260 (M+, 79), 231 (16), 217 (44), 215 (31), 190 (21),
189 (15), 187 (51), 173 (30), 159 (16), 157 (13), 146 (13), 145 (100), 143 (17), 131 (35), 130 (15), 129
(46), 128 (32), 127 (10), 117 (63), 116 (11), 115 (31), 91 (19); Anal. Calcd for C17H24O2; C, 78.42; H,
9.29. Found: C, 78.28; H, 9.14.
1-(4-Ethoxycarbonylphenyl)-2-methylpropene (entry 21). A colorless
oil, Rf 0.38 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz, CDCl3) δ
Me
Me
CO2Et
7.98 (d, J = 8.3 Hz, 2H), 7.28 (d, J = 8.3 Hz, 2H), 6.29 (s, 1H), 4.37 (q, J =
7.1 Hz, 2H), 1.93 (s, 3H), 1.88 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.6,
143.3, 137.9, 129.3, 128.5, 127.7, 124.6, 60.8, 27.1, 19.6, 14.3; IR (neat) 2980, 1715, 1607, 1410, 1366,
1275, 1178, 1103, 1020, 878, 760, 706 cm–1; MS (EI, 70 eV) m/z (%) 205 (M++1, 11), 204 (M+, 78),
160 (14), 159 (100), 131 (32), 116 (12), 115 (19), 91 (16); Anal. Calcd for C13H16O2; C, 76.44; H, 7.90.
Found: C, 76.24; H, 7.99.
(5E,7E)-Tetradeca-5,7-dienenitrile (entry 22). A colorless oil, Rf 0.42
(hexane–ethyl acetate = 5:1). 1H NMR (400 MHz, CDCl3) δ 6.11–5.94
NC
Hex
(m, 2H), 5.63 (dt, J = 14.6, 7.0 Hz, 1H), 5.46 (dt, J = 14.8, 7.0 Hz, 1H), 2.34 (t, J = 7.1 Hz, 2H), 2.22 (q,
J = 7.1 Hz, 2H), 2.06 (dt, J = 7.1, 7.0 Hz, 2H), 1.80–1.71 (m, 2H), 1.45–1.20 (m, 8H), 0.88 (t, J = 7.0
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 134.1, 132.6, 129.6, 128.5, 119.6, 32.6, 31.7, 31.2, 29.2, 28.9,
25.0, 22.6, 16.3, 14.1; IR (neat) 3017, 2957, 2926, 2855, 2247, 1456, 1437, 989, 733 cm–1; MS (EI, 70
eV) m/z (%) 206 (M++1, 10), 205 (M+, 59), 204 (M+–1, 13), 177 (37), 176 (34), 162 (13), 148 (36), 135
(16), 134 (100), 121 (29), 120 (60), 107 (15), 106 (16), 95 (15), 94 (26), 93 (52), 91 (25), 83 (21), 82
(10), 81 (67), 80 (45), 79 (39), 77 (22), 67 (45), 55 (15); Anal. Calcd for C14H23N; C, 81.89; H, 11.29.
Found: C, 82.18; H, 11.56.
(5E,7Z)-Tetradeca-5,7-dienenitrile (entry 23). A colorless oil, Rf 0.36
(hexane–ethyl acetate = 7:1). 1H NMR (400 MHz, CDCl3) δ 6.37 (ddq, J =
15.1, 10.9, 1.3 Hz, 1H), 5.94 (t, J = 10.9 Hz, 1H), 5.55 (dt, J = 15.0, 7.6 Hz,
Hex
NC
1H), 5.37 (dt, J = 10.9, 7.6 Hz, 1H), 2.35 (t, J = 7.1 Hz, 2H), 2.27 (m, 2H), 2.16 (m, 2H), 1.77 (m, 2H),
13
1.41–1.21(m, 8H), 0.88 (t, J = 6.9 Hz, 3H); C NMR (101 MHz, CDCl3) δ 131.7, 130.8, 127.84,
127.81, 119.6, 31.7, 31.5, 29.6, 28.9, 27.7, 25.0, 22.6, 16.4, 14.1; IR (neat) 3020, 2957, 2928, 2855,
S15

2247, 1456, 984, 949, 735 cm–1; MS (EI, 70 eV) m/z (%) 205 (M+, 43), 204 (M+–1, 11), 177 (51), 176
(40), 162 (14), 148 (40), 135 (15), 134 (100), 121 (30), 120 (70), 107 (16), 106 (19), 95 (16), 94 (29),
93 (50), 91 (26), 83 (31), 82 (12), 81 (79), 80 (53), 79 (44), 77 (25), 67 (53), 55 (19), 54 (10); Anal.
Calcd for C14H23N; C, 81.89; H, 11.29. Found: C, 82.19; H, 11.18.
Gram-scale cross-coupling reaction. To a mixture of K2CO3 (9.1 g, 66 mmol), tri(2-
furyl)phosphine (138 mg, 0.60 mmol), and PdCl2 (54 mg, 0.30 mmol) in DMSO (75 mL) were added
1a (9.1 g, 33 mmol) and ethyl 4-iodobenzoate (8.3 g, 30 mmol) sequentially, and the resulting mixture
was stirred at 35 °C for 21 h. The mixture was diluted with diethyl ether, washed with water and
brine, and dried over anhydrous MgSO4. Concentration in vacuo followed distillation under vacuum
(1.0 mmHg) gave cyclic silyl ether 3 (3.1 g, 62%); the residue was further purified by flash
chromatography on silica gel to give (E)-1-(4-ethoxycarbonylphenyl)-1-octene (7.6 g, 97%)
Cross-coupling of 2a–2d with aryl iodides. A general procedure. To a mixture of an
arylsilane
(0.81
mmol),
K2CO3
(194
mg,
1.4
mmol),
N-(2-
diphenylphosphinobenzylidene)cyclohexylamine (4) (10.4 mg, 28 µmol), and PdCl2 (3.7 mg, 21 µmol)
in DMSO (4.0 mL) were added an aryl iodide (0.7 mmol) and water (25 mg, 1.4 mmol) sequentially,
and the resulting mixture was stirred at 50 °C. After the time specified in Table 2, the mixture was
diluted with diethyl ether, washed with water and brine, and dried over anhydrous MgSO4.
Concentration in vacuo followed by flash chromatography on silica gel afforded the corresponding
coupling product in a yield listed in Table 2. The spectra of the biaryls shown in entries 1–5 agreed
well with those reported by us recently.5
4-Fluoro-4’-ethoxycarbonylbiphenyl (entry 6). A colorless solid (mp
64.6–65.4 °C), Rf 0.33 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CO2Et
CDCl3) δ 8.11 (d, J = 8.5 Hz, 2H), 7.64–7.55 (m, 4H), 7.16 (t, J = 8.8 Hz,
2H), 4.40 (q, J = 7.1 Hz, 2H), 1.42 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz,
F
CDCl3) δ 166.4, 162.9 (d, J = 247.7 Hz), 144.5, 136.2, 130.1, 129.2, 128.9 (d, J = 8.4 Hz), 126.8, 115.8
(d, J = 22.2 Hz), 61.0, 14.3; IR (KBr) 2990, 1717, 1599, 1528, 1495, 1367, 1279, 1238, 1190, 1113,
1026, 833, 772 cm–1; MS (EI, 70 eV) m/z (%) 245 (M++1, 10), 244 (M+, 60), 216 (23), 200 (17), 199
(100); Anal. Calcd for C15H13FO2; C, 73.76; H, 5.36. Found: C, 73.49; H, 5.34.
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4-Ethoxycarbonyl-2’-methylbiphenyl (entry 7). A colorless oil, Rf 0.19
(hexane–ethyl acetate = 20:1). 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.3
Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.31–7.21 (m, 4H), 4.41 (q, J = 7.1 Hz, 2H),
CO2Et
Me
13
2.27 (s, 3H), 1.42 (t, J = 7.1 Hz, 3H); C NMR (101 MHz, CDCl3) δ 166.6,
146.6, 140.9, 135.2, 130.5, 129.5, 129.4, 129.2, 128.9, 127.8, 125.9, 61.0, 20.4, 14.4; IR (neat) 2980,
1715, 1611, 1481, 1400, 1367, 1277, 1178, 1101, 1026, 1007, 858, 779, 754, 727, 708 cm–1; MS (EI, 70
eV) m/z (%) 241 (M++1, 14), 240 (M+, 77), 212 (15), 196 (18), 195 (100), 167 (30), 166 (16), 165 (39),
152 (25); Anal. Calcd for C16H16O2; C, 79.97; H, 6.71. Found: C, 79.83; H, 6.76.
2-(4-Ethoxycarbonylphenyl)thiophene (entry 8). A colorless solid (mp
66.3–67.3 °C), Rf 0.36 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CDCl3) δ 8.05 (d, J = 8.6 Hz, 2H), 7.67 (d, J = 8.6 Hz, 2H), 7.42 (d, J = 3.7 Hz,
CO2Et
S
1H), 7.36 (d, J = 5.1 Hz, 1H), 7.12 (dd, J = 5.1, 3.7 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7.1
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.3, 143.1, 138.5, 130.2, 129.1, 128.3, 126.2, 125.5, 124.4,
61.0, 14.3; IR (KBr) 3094, 3067, 2999, 2976, 2359, 1697, 1605, 1462, 1425, 1412, 1366, 1317, 1277,
1263, 1184, 1169, 1111, 1016, 862, 773, 727, 710, 698 cm–1; MS (EI, 70 eV) m/z (%) 233 (M++1, 10),
232 (M+, 84), 204 (25), 188 (15), 187 (100), 159 (13); Anal. Calcd for C13H12O2S; C, 67.21; H, 5.21.
Found: C, 67.01; H, 5.25.
References
(1) Yoshida, H.; Shirakawa, E.; Kurahashi, T.; Nakao, Y.; Hiyama, T. Organometallics 2000, 19,
5671–5678.
(2) Kant, J. J. Org. Chem. 1993, 58, 2296–2301.
(3) Hopkins, M. H.; Overman, L. E.; Rishton, G. M. J. Am. Chem. Soc. 1991, 113, 5354–5365.
(4) Frisell, C.; Lawesson, S.-O. Org. Synth. Coll. Vol. 1972, 5, 642–644.
(5) Sahoo, A. K.; Oda, T.; Nakao, Y.; Hiyama, T. Adv. Synth. Catal. 2004, 346, 1715–1727.
S17