Palladium-Catalyzed Coupling Reactions
Organometallics, Vol. 20, No. 13, 2001 2919
commercially available. Solvents were purified by standard
methods before use.
2-(1,1′-Bip h en yl-2-yl)-1-(2-th ien yl)eth a n on e: 1H NMR δ
7.56 (dd, 1 H, J ) 0.96, 4.9 Hz), 7.27-7.40 (m, 10 H), 7.00 (dd,
1 H, J ) 4.0, 4.9 Hz), 4.17 (s, 2 H); 13C NMR δ 190.9, 143.9,
142.3, 141.2, 133.7, 132.2, 132.0, 130.6, 130.1, 129.2, 128.2,
127.9, 127.6, 127.2, 127.1, 43.7; MS m/ z 278 (M+). Anal. Calcd
for C18H14OS: C, 77.67; H, 5.07. Found: C, 77.62; H, 5.35.
1-(1,1′-Biph en yl-2-yl)-3,3-dim eth ylbu tan -2-on e:16 1H NMR
δ 7.24-7.37 (m, 5 H), 7.18-7.25 (m, 3 H), 7.14-7.16 (m, 1 H),
3.77 (s, 2 H), 0.99 (s, 9 H); 13C NMR δ 213.3, 142.5, 141.5,
132.7, 130.9, 129.9, 129.1, 128.1, 127.3, 127.0, 126.7, 44.3, 41.5,
26.5; MS m/ z 252 (M+).
Ca ta lytic Cr oss-Cou p lin g of Bip h en ylen e (1) w ith
Olefin s 2. A mixture of 1 (15 mg, 0.1 mmol), 2 (0.13 mmol),
Pd(PPh3)4 (6 mg, 0.005 mmol), p-cresol (11 mg, 0.1 mmol), and
C6D6 (0.7 cm3) was placed in a resealable NMR tube. An N2
atmosphere was charged, and the mixture was heated at 120
°C for 6 days. After cooling, the products were isolated by thin-
layer chromatography on silica gel using hexanes-ethyl
acetate as eluent.
Bu tyl 3-(1,1′-bip h en yl-2-yl)-2-p r op en oa te (E:Z ) 87:13):
1H NMR δ 7.71 (d, 1 H, J ) 15.9 Hz, E), 7.68-7.70 (m, 1 H),
7.34-7.44 (m, 6 H), 7.28-7.31 (m, 2 H), 6.83 (d, 1 H, J ) 12.2
Hz, Z), 6.38 (d, 1 H, J ) 15.9 Hz, E), 5.91 (d, 1 H, J ) 12.2 Hz,
Z), 4.13 (t, 2 H, J ) 6.6 Hz, E), 4.07 (t, 2 H, J ) 6.6 Hz, Z),
1.58-1.65 (m, 2 H, E), 1.49-1.54 (m, 2 H, Z), 1.31-1.41 (m, 2
H, E), 1.21-1.27 (m, 2 H, Z), 0.91 (t, 3 H, J ) 7.4 Hz, E), 0.85
(t, 3 H, J ) 7.4 Hz, Z); 13C NMR δ 166.9, 143.6, 142.9, 139.9,
132.6, 130.5, 129.8 (overlapped), 128.2, 127.6, 127.5, 126.7,
119.1, 64.2, 30.7, 19.1, 13.7; MS m/ z 280 (M+). Anal. Calcd
for C19H20O2: C, 81.40; H, 7.19. Found: C, 81.21; H, 7.35.
(E)-2-[2-(4-Meth ylp h en yl)eth en yl]-1,1′-bip h en yl:14 1H
NMR δ 7.75 (d, 1 H, J ) 7.6 Hz), 7.32-7.44 (m, 8 H), 7.26 (d,
2 H, J ) 8.1 Hz), 7.10 (d, 2 H, J ) 8.1 Hz), 7.07 (d, 1 H, J )
16.2 Hz), 7.01 (d, 1 H, J ) 16.2 Hz), 2.32 (s, 3 H); 13C NMR δ
141.0, 140.9, 137.4, 135.6, 134.8, 130.3, 130.0, 129.4, 129.3,
128.1, 127.5, 127.3, 127.0, 126.8, 126.4, 125.7, 21.2; MS m/ z
270 (M+).
(1,1′-Bip h en yl-2-yl)(4-m eth ylp h en yl)a ceton itr ile (13):
1H NMR δ 7.47-7.49 (m, 1 H), 7.33-7.44 (m, 5 H), 7.24-7.29
(m, 3 H), 7.07 (d, 2 H, J ) 8.1 Hz), 6.98 (d, 2 H, J ) 8.1 Hz),
5.26 (s, 1 H), 2.29 (s, 3 H); 13C NMR δ 141.6, 139.9, 137.7,
133.9, 133.2, 130.5, 129.5, 129.2, 128.8, 128.6, 128.5, 128.1,
127.8, 127.4, 120.4, 38.6, 21.0; MS m/ z 283 (M+). Anal. Calcd
for C21H17N: C, 89.01; H, 6.05; N, 4.94. Found: C, 88.68; H,
5.87; N, 5.25.
P r ep a r a tion of tr a n s-P h (AcO)P d (P P h 3)2 (9a ). A mixture
of trans-Ph(I)Pd(PPh3)2 (83 mg, 0.1 mmol), silver acetate (17
mg, 0.1 mmol), and THF (4 cm3) was stirred under N2 at room
temperature for 1 h. After addition of THF (4 cm3), the
supernatant was separated and then dried under vacuum. A
gray solid was obtained (76 mg, 99%). A trace of the starting
complex was also present and was not separated: 1H NMR
(THF-d8) δ 7.43-7.44 (m, 12 H), 7.32 (t, 6 H, J ) 7.4 Hz), 7.23
(t, 12 H, J ) 7.4 Hz), 6.55 (d, 2 H, J ) 7.5 Hz), 6.48 (t, 1 H, J
) 7.5 Hz), 6.25 (t, 2 H, J ) 7.5 Hz), 0.79 (s, 3 H);17 31P NMR
(THF-d8) δ 19.1.
P r ep a r a tion of tr a n s-P h (p-MeC6H4O)P d (P P h 3)2 (9b). A
mixture of 9a (38 mg, 0.05 mmol), sodium p-cresolate (7 mg,
0.05 mmol), and THF (4 cm3) was stirred under N2 at room
temperature for 1 h. After addition of THF (1 cm3), the
suspension was filtered to remove a white solid. The solvent
was removed under vacuum to give a yellow powder. Recrys-
tallization from toluene/hexane gave yellow microcrystals (21
mg, 52%). A small amount of 9a was also present and was not
separated (9a :9b ) 1:9): 1H NMR (THF-d8) δ 7.43-7.48 (m,
12 H), 7.26 (t, 6H, J ) 7.4 Hz), 7.14 (t, 12 H, J ) 7.4 Hz), 6.71
(dd, 2 H, J ) 1.4, 7.9 Hz), 6.36 (t, 1 H, J ) 7.3 Hz), 6.21-6.27
(m, 4 H), 6.10 (d, 2 H, J ) 6.5 Hz), 1.93 (s, 3 H); 31P NMR
(THF-d8) δ 15.5.
(E)-2-(2-P h en yleth en yl)-1,1′-bip h en yl:14 1H NMR δ 7.76
(d, 1 H, J ) 7.5 Hz), 7.33-7.45 (m, 10 H), 7.29 (t, 2 H, J ) 7.2
Hz), 7.21 (t, 1 H, J ) 7.2 Hz), 7.12 (d, 1 H, J ) 16.3 Hz), 7.04
(d, 1 H, J ) 16.3 Hz); 13C NMR δ 141.1, 140.9, 137.6, 135.4,
130.3, 130.0, 129.4, 128.6, 128.1, 127.8, 127.6, 127.5, 127.5,
127.1, 126.5, 125.8; MS m/ z 256 (M+).
Ca ta lytic Cr oss-Cou p lin g of Bip h en ylen e (1) w ith
Ar ylbor on ic Acid s 5. The procedures were essentially the
same as those for the reaction with 2, other than the reaction
time (2.5-18 h).
4-Meth oxy-1,1′:2′,1′′-ter p h en yl:15 1H NMR δ 7.37-7.42 (m,
4 H), 7.19-7.23 (m, 3 H), 7.14-7.17 (m, 2 H), 7.05 (d, 2 H, J
) 8.7 Hz), 6.75 (d, 2 H, J ) 8.7 Hz), 3.76 (s, 3 H); 13C NMR δ
158.3, 141.7, 140.4, 140.1, 133.9, 130.9, 130.6, 130.5, 129.8,
127.9, 127.4, 127.1, 126.3, 113.3, 55.1; MS m/ z 260 (M+).
1,1′:2′,1′′-Ter p h en yl:15 1H NMR δ 7.39-7.44 (m, 4 H),
7.18-7.21 (m, 6 H), 7.12-7.14 (m, 4 H); 13C NMR δ 141.5,
140.5, 130.6, 129.9, 127.8, 127.5, 126.4; MS m/ z 230 (M+).
4-F lu or o-1,1′:2′,1′′-ter p h en yl:15 1H NMR δ 7.39-7.41 (m,
4 H), 7.17-7.23 (m, 3 H), 7.05-7.12 (m, 4 H), 6.87-6.92 (m, 2
H); 13C NMR δ 161.7 (d, J C-F ) 245.3 Hz), 141.3, 140.6, 139.5,
137.4, 131.3 (d, J C-F ) 7.8 Hz), 130.6, 130.5, 129.8, 127.9,
127.6, 127.5, 126.5, 114.8 (d, J C-F ) 21.2 Hz); MS m/ z 248
(M+).
Stoich iom etr ic Rea ction of tr a n s-P h (X)P d (P P h 3)2 (9)
w ith Acetop h en on e. A mixture of 9 (0.01 mmol), acetophe-
none (12 mg, 0.1 mmol), and THF-d8 (0.7 cm3) was heated
under N2 (1 atm) at 50 or 80 °C for 18-21 days. The time
course of the reaction was monitored by 1H and 31P NMR
spectroscopy.
Ca ta lytic Cr oss-Cou p lin g of Bip h en ylen e (1) w ith
Keton es 7 a n d Nitr ile 12. A mixture of 1 (15 mg, 0.1 mmol),
7 or 12 (0.1-0.3 mmol), Pd(PPh3)4 (6 mg, 0.005 mmol), p-cresol
(1 mg, 0.01 mmol), and C6D6 (0.7 cm3) was placed in a
resealable NMR tube. An N2 atmosphere was charged, and
the mixture was heated at 120 °C for 7 h to 3 days. After
cooling, the products were isolated by thin-layer chromatog-
raphy on silica gel using hexanes-ethyl acetate as eluent.
2-(1,1′-Biph en yl-2-yl)-1-ph en yleth an on e: 1H NMR δ 7.76-
7.79 (m, 2 H), 7.47-7.52 (m, 1 H), 7.26-7.39 (m, 11 H), 4.24
(s, 2 H); 13C NMR δ 198.3, 142.3, 141.3, 136.6, 133.0, 132.3,
130.6, 130.2, 129.1, 128.5, 128.3, 128.2, 127.6, 127.1, 127.0,
43.2; MS m/ z 272 (M+). Anal. Calcd for C20H16O: C, 88.20; H,
5.92. Found: C, 88.27; H, 5.88.
Ack n ow led gm en t. This work was supported by the
U.S. Department of Energy (Grant FG02-86ER13569)
and by a scholarship from the Ministry of Education,
Science, Sports and Culture, J apan, to T.S.
OM010196R
(14) Peter, H. G.; op het Veld; Laarhoven, W. H. J . Chem. Soc.,
Perkin Trans. 2 1978, 915.
(15) Sato, T.; Shimada, S.; Hata, K. Bull. Chem. Soc. J pn. 1969,
42, 766.
(16) Bunnett, J . F.; Mitchel, E.; Galli, C. Tetrahedron 1985, 41, 4119.
(17) For other examples of acetate resonances observed upfield of
that typical of acetate, see: Albert, J .; Granell, J .; Moragas, R.; Font-
Bard´ıa, M.; Solans, X. J . Organomet. Chem. 1996, 522, 59.