Ito et al.
temperature, and iodomethane (1.34 mmol) was added. The
mixture was stirred for 3 h, and the solvent was removed in
vacuo. The residue was extracted with hexane and subjected
to silica gel column chromatography (hexane/AcOEt ) 100:1)
to afford 270 mg of 2a (82% yield): pale yellow solids, mp
afford 12 mg of 4 (5% yield) and a trace amount of 5. 3: yellow
plates (hexane), mp 205-206 °C; 31P{1H} NMR (162 MHz,
CDCl3) δ 54.5 (d, 2J PP ) 25 Hz, P1), 23.5 (d, 2J PP ) 25 Hz, P2);
1H NMR (400 MHz, CDCl3) δ 7.53 (2H, m, m-Mes*), 7.49 (2H,
m, m-Mes*), 7.15 (5H, m, Ph), 6.90 (3H, m, Ph),); 6.81 (1H,
3
71-73 °C; 31P NMR (162 MHz, CDCl3) δ 259.9 (d, J PH ) 13
dd, 3J PH ) 38 Hz, 3J PH ) 13 Hz, C(H)Ph), 6.48 (1H, dd, 2J PH
)
Hz); 1H NMR (400 MHz, CDCl3) δ 7.4-7.6 (7H, m, arom), 5.33
17 Hz, J PH ) 6 Hz, dCH), 6.36 (2H, m, Ph), 1.65 (36H, s,
3
3
(1H, d, J PH ) 13 Hz, CH), 3.52 (3H, s, OMe), 1.61 (9H, s,
o-tBu), 1.36 (18H, s, p-tBu); 13C{1H} NMR (101 MHz, CDCl3)
o-tBu), 1.42 (9H, s, o-tBu), 1.41 (9H, s, p-tBu); 13C{1H} NMR
δ 138.5 (dd, J PC ) 19 Hz, J PC ) 3 Hz, ipso-Ph), 138.4 (dd,
3 1
2
3
1
(101 MHz, CDCl3) δ 166.2 (d, J PC ) 64 Hz, PdC), 154.2 (s,
3J PC ) 9 Hz, J PC ) 3 Hz, ipso-Ph), 135.0 (dd, J PC ) 28 Hz,
1 1
3
o-Mes*), 153.9 (s, o-Mes*), 151.4 (s, p-Mes*), 139.8 (d, J PC
)
2J PC ) 23 Hz, PCPh), 134.8 (dd, J PC ) 42 Hz, J PC ) 35 Hz,
1 3
1
11 Hz, ipso-Ph), 137.1 (d, J PC ) 54 Hz, ipso-Mes*), 128.5 (s,
o-Ph), 128.4 (s, p-Ph), 127.8 (s, m-Ph), 123.0 (s, m-Mes*), 122.6
(s, m-Mes*), 89.1 (d, 2J PC ) 37 Hz, CH), 57.7 (s, OMe), 38.5 (s,
PCP), 129.3 (dd, J PC ) 61 Hz, J PC ) 3 Hz, ipso-Mes*), 128.8
1 3
(dd, J PC ) 60 Hz, J PC ) 1 Hz, ipso-Mes*), 128.2 (s, o-Ph),
2
2
128.0 (s, o-Ph), 127.9 (dd, J PC ) 6 Hz, J PC ) 4 Hz, CHPh),
4
1
2
o-CMe3), 35.6 (s, p-CMe3), 33.7 (d, J PC ) 7 Hz, o-CMe3), 33.4
127.3 (dd, J PC ) 23 Hz, J PC ) 10 Hz, dCH), 127.2 (s, m-Ph),
127.2 (s, p-Ph), 31.6 (s, p-CMe3), 125.8 (s, m-Mes*), 40.2 (d,
4
(d, J PC ) 6 Hz, o-CMe3), 32.1 (s, p-CMe3); EI-MS m/z (rel
intensity) 489 (M+ + 1; 0.6%), 487 (M+ - 1; 0.6%), 475 (M+
-
3J PC ) 4 Hz, o-CMe3), 40.0 (d, J PC ) 4 Hz, o-CMe3), 35.3 (s,
3
Me + 2; 1%), 473 (M+ - Me; 1%), 459 (M+ - OMe + 2; 30%),
457 (M+ - OMe; 30%), 409 (M+ - Br; 33%), 377 (M+ - Br -
OMe + 1; 57%), 219 (Mes*P+ - tBu; 100%); HRMS calcd for
p-CMe3), 35.2 (s, p-CMe3), 34.4 (d, J PC ) 6 Hz, o-CMe3), 33.9
4
4
(d, J PC ) 3 Hz, o-CMe3), 31.7 (s, p-CMe3); UV (CH2Cl2) λmax
/
nm (log ꢀ) 256 (4.61), 417 (3.97). Anal. Calcd for C52H70P2: C
82.50, H 9.32. Found: C 82.32, H 9.28.
C
27H3878BrOP - H 487.1760; found 487.1756.
Com p ou n d 2b. To a solution of Mes*PdCBr2 (230 mg, 0.51
Com p ou n d 9. To a solution of 2a (322 mg, 0.66 mmol) in
THF (20 mL) was added LDA (ca. 0.66 mmol, prepared from
diisopropylamine and butyllithium at 0 °C in THF) at -78 °C,
and the mixture was stirred for 15 min. The mixture was
warmed to 0 °C and stirred for 1 h. After warming up to room
temperature, the solvent was removed in vacuo, and the
residue was extracted with hexane. The solution was concen-
trated and the residual solid was recrystallized from ethanol
to afford 69 mg of 9 (26% yield): pale yellow crystals, mp 139-
142 °C; 31P{1H} NMR (162 MHz, CDCl3) δ 144.0; 1H NMR (400
MHz, CDCl3) δ 7.3-7.6 (7H, m, arom), 3.66 (3H, s, OMe), 1.60
(18H, s, o-tBu), 1.35 (9H, s, p-tBu); 13C{1H} NMR (101 MHz,
mmol) in THF (15 mL) was added butyllithium (0.51 mmol)
at -78 °C, and the mixture was stirred for 15 min. The
reaction mixture was treated with benzyl bromide (0.51 mmol)
and warmed to room temperature. The solvent was removed
in vacuo, and the residue was extracted with hexane. The
solution was subjected to silica gel column chromatography
(hexane) to afford 150 mg of 2b (64% yield): pale yellow
needles (EtOH), mp 117-119 °C; 31P NMR (162 MHz, CDCl3)
3
δ 248.2 (t, J PH ) 21 Hz); 1H NMR (400 MHz, CDCl3) δ
3
7.3-7.6 (7H, m, arom), 4.15 (2H, d, J PH ) 21 Hz, CH2), 1.48
(18H, s, o-tBu), 1.34 (9H, s, p-tBu); 13C{1H} NMR (101 MHz,
1
2
1
2
CDCl3) δ 165.2 (d, J PC ) 61 Hz, PdC), 153.8 (d, J PC ) 2 Hz,
CDCl3) δ 229.2 (d, J PC ) 19 Hz, PdCdC), 154.1 (d, J PC ) 4
3
o-Mes*), 151.3 (s, p-Mes*), 138.7 (d, J PC ) 13 Hz, ipso-Ph),
Hz, o-Mes*), 151.9 (d, 3J PC ) 3 Hz, ipso-Ph), 150.1 (s, p-Mes*),
1
1
2
138.7 (d, J PC ) 53 Hz, ipso-Mes*), 130.0 (s, o-Ph), 128.8 (s,
136.1 (d, J PC ) 74.8 Hz, ipso-Mes*), 133.8 (d, J PC ) 7 Hz,
PdCdC), 129.1 (s, p-Ph), 128.4 (s, m-Ph), 127.8 (s, o-Ph), 122.6
(s, m-Mes*), 58.1 (s, OMe), 38.6 (s, o-CMe3), 35.4 (s, p-CMe3),
34.2 (d, 4J PC ) 7 Hz, o-CMe3), 31.8 (s, p-CMe3). Anal. Calcd for
2
m-Ph), 127.4 (s, p-Ph), 122.7 (s, m-Mes*), 50.7 (d, J PC ) 33
4
Hz, CH2), 38.5 (s, o-CMe3), 35.7 (s, p-CMe3), 33.4 (d, J PC ) 7
Hz, o-CMe3), 32.1 (s, p-CMe3). Anal. Calcd for C26H36BrP: C
67.96, H 7.91, Br 17.39. Found: C 68.14, H 7.83, Br 17.37.
P r ep a r a tion of 3. F r om 2a . To a solution of 2a (170 mg,
0.35 mmol) in THF (15 mL) was added tert-butyllithium (0.36
mmol, 1.5 M solution in pentane) at -100 °C, and the mixture
was stirred for 15 min. The mixture was warmed to room
temperature, and the solvent was removed in vacuo. The
residue was extracted in hexane, and the solution was
concentrated. The residual solids were recrystallized from
hexane to afford 41 mg of 3 (31% yield). The filtrate was
subjected to silica gel column chromatography (hexane) to
afford 3 mg of 4 (2% yield) and 9 mg of 5 (6% yield). F r om 2b.
To a solution of 2b (303 mg, 0.66 mmol) in THF (20 mL) was
added potassium tert-butoxide (1.32 mmol, dissolved in 10 mL
of THF) at 0 °C, and the mixture was stirred for 15 min. The
mixture was warmed to room temperature, and the solvent
was removed in vacuo. The residue was extracted in hexane,
and after concentration the residual solid was recrystallized
from hexane to afford 93 mg of 3 (37% yield). The filtrate was
subjected to silica gel column chromatography (hexane) to
C
27H37OP: C 79.35, H 9.15. Found: C 79.37, H 8.92.
X-r a y Cr ysta llogr a p h y. Single crystals were obtained by
recrystallization from
a mixture of hexane and dichlo-
romethane at 0 °C (for 3) or from ethanol at room temperature
(for 9). Crystallographic data (excluding structure factors) for
the structures reported in this paper have been deposited with
the Cambridge Crystallographic Data Centre as supplemen-
tary publications no. CCDC-230188 (3) and -230189 (9).
Ack n ow led gm en t. This work was supported in part
by Grants-in-Aid for Scientific Research (13304049 and
14044012) from the Ministry of Education, Culture,
Sports, Science and Technology, J apan.
Su p p or tin g In for m a tion Ava ila ble: Comments in Fig-
ures 1-3 and CIF files for 3 and 9. This material is available
J O0497407
4184 J . Org. Chem., Vol. 69, No. 12, 2004