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LETTER
H+] calcd for C48H33O2P2: 703.1956; found: 703.1962.
(ii) Synthesis of 21: To a flask were added 19 (1.01 g, 2.0
mmol), 1,3-dibromobenzene (300 mg, 0.91 mmol),
(7) In phosphination step, polar by-products were observed at
the bottom on TLC, and so we are trying to avoid the by-
product formation: van Assema, S. G. A.; Tazelaar, C. G. J.;
Bas de Jong, G.; van Maarseveen, J. H.; Schakel, M.; Lutz,
M.; Spek, A. L.; Slootweg, J. C.; Lammertsma, K.
Organometallics 2008, 27, 3210.
(8) (a) Fang, J.-K.; An, D.-L.; Wakamatsu, K.; Ishikawa, T.;
Iwanaga, T.; Toyota, S.; Akita, S.-I.; Matsuo, D.; Orita, A.;
Otera, J. Tetrahedron 2010, 66, 5479. (b) Fang, J.-K.; An,
D.-L.; Wakamatsu, K.; Ishikawa, T.; Iwanaga, T.; Toyota,
S.; Matsuo, D.; Orita, A.; Otera, J. Tetrahedron Lett. 2010,
51, 917.
(9) Yang, X.; Fang, J.-K.; Suzuma, Y.; Xu, F.; Orita, A.; Otera,
J.; Kajiyama, S.; Koumura, N.; Hara, K. Chem. Lett. 2011,
40, 620.
(10) An, D.-L.; Nakano, T.; Orita, A.; Otera, J. Angew. Chem. Int.
Ed. 2002, 41, 171.
Pd(PPh3)4 (104 mg, 0.09 mmol), CuI (17.1 mg, 0.09 mmol),
diisopropylamine (5 mL) and toluene (25 mL), and the
mixture was stirred under nitrogen at 80 °C for 20 h. After
workup with EtOAc–H2O, the organic layer was washed
with aq NH4Cl and brine, and dried over MgSO4. After
filtration, the solvents were evaporated. The crude product
was subjected to column chromatography on silica gel
(EtOAc) to give 21 (0.96 g, 98% yield) in a pure form.
Compound 21: 1H NMR (500 MHz, CDCl3): d = 6.48 (s, 1
H), 6.53 (d, J = 7.9 Hz, 2 H), 6.84 (t, J = 7.9 Hz, 1 H), 7.03–
7.09 (m, 4 H), 7.11–7.15 (m, 4 H), 7.17–7.26 (m, 8 H), 7.31–
7.39 (m, 12 H), 7.45–7.56 (m, 4 H), 7.70 (d, J = 8.3 Hz, 2 H),
7.80 (d, J = 8.6 Hz, 2 H), 7.90 (d, J = 8.3 Hz, 2 H), 7.94–7.97
(m, 6 H). 13C NMR (75 MHz, CDCl3): d = 84.23, 86.49,
91.00 (d, J = 306.0 Hz), 104.29 (d, J = 29.6 Hz), 118.25 (d,
J = 4.0 Hz), 121.43, 122.59, 126.15, 126.40, 126.81, 127.17,
127.64, 127.83, 128.11, 128.17 (d, J = 13.3, 13.6 Hz),
128.39, 128.47, 130.17, 130.32 (d, J = 11.8, 11.4 Hz),
130.84, 131.48, 131.65 (d, J = 2.5, 2.5 Hz), 131.77, 132.24,
132.77, 132.82, 132.91 (d, J = 125.9, 125.9 Hz), 133.38,
138.90, 142.08. HRMS: m/z [M + H+] calcd for C78H49O2P2:
1079.3208; found: 1079.3196.
(iii) Synthesis of 22: To a flask were added 21 (534 mg, 0.50
mmol), t-BuOK (167 mg, 1.5 mmol) and THF (10 mL), and
the mixture was stirred under nitrogen at r.t. for 15 h. After
workup with CH2Cl2–H2O, the organic layer was washed
with brine and dried over Na2SO4. After filtration, the
solvents were evaporated, and the crude product was
subjected to column chromatography on silica gel (hexane–
CH2Cl2, 1:1) to give 22 (246 mg, 73% yield) in a pure form.
Compound 22: 1H NMR (300 MHz, CDCl3): d = 2.79 (s, 2
H), 6.44 (s, 1 H), 6.50 (dd, J = 1.6, 7.8 Hz, 2 H), 6.84 (t, J =
7.5 Hz, 1 H), 7.18–7.33 (m, 8 H), 7.44–7.53 (m, 4 H), 7.74
(d, J = 9.3 Hz, 4 H), 7.94 (q, J = 7.9 Hz, 8 H). 13C NMR (75
MHz, CDCl3): d = 80.79, 82.80, 89.51, 92.67, 120.44,
121.26, 122.99, 126.26, 126.39, 126.55, 126.70, 126.81,
127.70, 128.01, 128.03, 128.05, 128.12, 128.86, 130.73,
132.34, 132.39, 132.90, 133.03, 133.62, 139.90, 140.60.
(iv) Synthesis of 15: To a flask were added 22 (68 mg, 0.1
mmol), 1,3-diiodobenzene (33 mg, 0.1 mmol), Pd(PPh3)4
(12 mg, 0.01 mmol), CuI (2 mg, 0.01 mmol), diisopropyl-
amine (5 mL) and toluene (45 mL), and the mixture was
stirred under nitrogen at 70 °C for 60 h. After workup with
CH2Cl2–H2O, the organic layer was washed with aq NH4Cl
and brine, and dried over MgSO4. After filtration, the
solvents were evaporated. The crude product was subjected
to column chromatography on silica gel (hexane–CH2Cl2,
4:1) to give 15 (16 mg, 22% yield) in a pure form as a white
powder. Compound 15: 1H NMR (500 MHz, CDCl3): d =
6.89–6.95 (m, 6 H), 7.05 (d, J = 8.5 Hz, 4 H), 7.22 (t, J = 7.0
Hz, 4 H), 7.42 (t, J = 7.0 Hz, 4 H), 7.76 (d, J = 8.5 Hz, 4 H),
7.86 (d, J = 8.5 Hz, 4 H), 7.87 (d, J = 8.5 Hz, 4 H), 7.92 (s,
2 H). 13C NMR (125 MHz, CDCl3): d = 90.4, 92.1, 121.8,
123.6, 126.4, 126.7, 126.8, 128.1, 128.2, 129.2, 129.6,
132.7, 133.0, 136.9, 138.6.
(11) (a) Tsumatori, H.; Nakashima, T.; Kawai, T. Org. Lett. 2010,
12, 2362. (b) Kawai, T.; Kawamura, K.; Tsumatori, H.;
Ishikawa, M.; Naito, M.; Fujiki, M.; Nakashima, T.
ChemPhysChem. 2007, 8, 1465.
(12) Synthesis of 15:
(i) Synthesis of 19: To a flask were added 18 (1.51 g, 5.0
mmol), Ph2PCl (0.92 mL, 5.0 mmol), CuI (95.2 mg, 0.5
mmol), toluene (20 mL) and Et3N (1.4 mL), and the mixture
was stirred under nitrogen at 80 °C for 19 h. After EtOAc
had been added, the mixture was filtered, and the filtrate was
washed with 10% NH3 (aq) and brine, and dried over
Na2SO4. After filtration, the solvents were evaporated, and
the crude product was subjected to the next reaction. To a
flask were added the crude products, 30% aq H2O2 (5.0 mL)
and THF (25 mL) at 0 °C, and the mixture was stirred at 0 °C
for 0.5 h and then at r.t. for 3 h. After workup with CH2Cl2–
H2O, the organic layer was washed with brine and dried over
Na2SO4. After filtration, the solvents were evaporated and
the crude product was subjected to column chromatography
on silica gel (Daisogel IR-60-63/210, EtOAc) to give 19
(1.35 g, 54% yield) and 20 (0.83 g, 24% yield). Compound
19: 1H NMR (300 MHz, CDCl3): d = 2.81 (s, 1 H), 7.02–7.22
(m, 6 H), 7.31–7.39 (m, 6 H), 7.42–7.46 (m, 2 H), 7.52–7.57
(m, 2 H), 7.70 (d, J = 8.6 Hz, 1 H), 7.79 (d, J = 8.6 Hz, 1 H),
7.95 (q, J = 8.3 Hz, 4 H). 13C NMR (100 MHz, CDCl3): d =
81.55, 82.11, 85.48 (d, J = 169.7 Hz), 104.20 (d, J = 30.5
Hz), 118.30 (d, J = 4.8 Hz), 120.64, 126.21, 126.34, 126.96,
127.23, 127.69, 127.98, 128.13, 128.24 (d, J = 13.6, 13.6
Hz), 128.48, 128.78, 130.21, 130.51 (d, J = 11.5, 11.5 Hz),
131.50, 131.70 (d, J = 2.8, 2.8 Hz), 132.02, 132.22, 132.72,
133.05 (d, J = 121.0, 121.0 Hz), 133.00, 133.82, 139.54,
141.88. HRMS: m/z [M + H+] calcd for C36H24OP: 503.1565;
found: 503.1555. Compound 20: 1H NMR (300 MHz,
CDCl3): d = 6.93–7.01 (m, 4 H), 7.07–7.13 (m, 4 H), 7.19–
7.41 (m, 16 H), 7.61 (t, J = 8.2 Hz, 2 H), 7.74 (d, J = 8.6 Hz,
2 H), 7.96 (t, J = 8.9 Hz, 4 H). 13C NMR (75 MHz, CDCl3):
d = 86.37 (d, J = 166.8 Hz), 103.25 (d, J = 29.3 Hz), 118.35
(d, J = 4.0 Hz), 126.23, 127.69, 127.99, 128.12, 128.30 (d,
J = 13.0, 13.6 Hz), 128.80, 130.03, 130.21 (d, J = 11.7, 11.5
Hz), 131.59, 131.83, 131.87, 132.16, 132.38 (d, J = 120.9,
120.9 Hz), 133.68, 141.04 (d, J = 2.2 Hz). HRMS: m/z [M +
Synlett 2011, No. 16, 2402–2406 © Thieme Stuttgart · New York