S. Ishikawa, K. Manabe / Tetrahedron 66 (2010) 297–303
303
129.32 (d, J¼79.2 Hz), 129.65, 130.69, 131.55 (d, J¼8.2 Hz), 132.84 (d,
J¼8.3 Hz), 143.46 (d, J¼6.6 Hz), 144.42, 148.49 ppm; 31P NMR
signal (C–P) was not observed due to broadening); 31P NMR
(162 MHz, CD3OD)
d
17.12 (br t, J¼67 Hz (P–D)) ppm; IR (ATR) 3406,
(202 MHz, CDCl3)
d
48.08 ppm; IR (ATR) 2929, 2856, 1417, 1198,
2935, 2854, 1448, 1061, 1005, 768 cmꢁ1; HRMS (ESI) m/z calcd for
C30H34OP ([MꢁH]ꢁ) 441.2353; found: 441.2350; Anal. Calcd for
C30H36BF4OP: C, 67.94; H, 6.84, found: C, 67.90; H, 6.93%.
1146, 904, 814, 764 cmꢁ1; HRMS (ESI) m/z calcd for C25H31F3O4PS
([MþH]þ) 515.1627; found: 515.1643; Anal. Calcd for C25H30F3O4PS:
C, 58.36; H, 5.88, found: C, 58.38; H, 5.95%.
Acknowledgements
4.4. Compound 28: Suzuki–Miyaura coupling of 23a with 3c
This work was partly supported by the Society of Synthetic Or-
ganic Chemistry, Japan and a Grant-in-Aid for Scientific Research on
Priority Areas ‘Advanced Molecular Transformations of Carbon
Resources’ from the Ministry of Education, Culture, Sports, Science
and Technology, Japan.
Triflate 23a (713 mg, 1.39 mmol), 3c (216 mg, 1.80 mmol), KF
(266 mg, 4.57 mmol), Pd(OAc)2 (6.1 mg, 0.0277 mmol), and
X-PHOS (15.9 mg, 0.0333 mmol) were placed in a flask, and then
evacuated and backfilled with argon. A THF/H2O (4/1) solution
(1.39 mL) was added at rt, and the whole was then stirred at rt for
13 h. The mixture was diluted with water (10 mL), and the product
was extracted with EtOAc (20 mL) and CH2Cl2 (20 mLꢂ2). The
combined organic layers were dried over Na2SO4 and concen-
trated. Recrystallization from hexane/CH2Cl2/MeOH and purifica-
tion of the mother liquid by column chromatography (silica gel,
chloroform/MeOH¼30/1) gave the desired product (28) as a white
solid in 95% yield (603 mg). Mp 261.8–265.0 (dec) ꢀC; 1H NMR
Supplementary data
Supplementary data associated with this article can be found in
References and notes
1. Ishikawa, S.; Manabe, K. Chem. Lett. 2007, 36, 1302.
(400 MHz, CDCl3/CD3OD¼10/1)
d 1.09–1.84 (22H, m), 6.89 (1H, t,
2. Examples of oligoarene-type phosphines: (a) Yu, H.-B.; Hu, Q.-S.; Pu, L. J. Am.
Chem. Soc. 2000, 122, 6500; (b) Goto, K.; Ohzu, Y.; Sato, H.; Kawashima, T. Phos-
phorus, Sulfur and Silicon 2002, 177, 2179; (c) Matsumoto, T.; Kasai, T.; Tatsumi, K.
Chem. Lett. 2002, 31, 346; (d) Iwasawa, T.; Komano, T.; Tajima, A.; Tokunaga, M.;
Obora, Y.; Fujihara, T.; Tsuji, Y. Organometallics 2006, 25, 4665; (e) Matsui, K.;
Takizawa, S.; Sasai, H. Synlett 2006, 761; (f) Ashburn, B. O.; Carter, R. G.; Zakharov,
L. N. J. Am. Chem. Soc. 2007, 129, 9109; Examples of hydroxylated phosphines: (g)
Hayashi, T.; Mise, T.; Kumada, M. Tetrahedron Lett.1976,17, 4351; (h) Hatanaka, Y.;
Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron Lett. 1994, 35, 7981; (i) Yoshikai,
N.; Mashima, H.; Nakamura, E. J. Am. Chem. Soc. 2005, 127, 17978.
3. (a) Tomori, H.; Fox, J. M.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5334; (b) Kaye, S.;
Fox, J. M.; Hicks, F. A.; Buchwald, S. L. Adv. Synth. Catal. 2001, 343, 789; (c) Barder,
T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005,127, 4685.
4. (a) Ishikawa, S.; Manabe, K. Chem. Lett. 2007, 36, 1304; (b) Ishikawa, S.; Manabe,
K. Org. Lett. 2007, 9, 5593; (c) Ishikawa, S.; Manabe, K. Synthesis 2008, 3180.
5. (a) Ishikawa, S.; Manabe, K. Chem. Lett. 2006, 35, 164; (b) Ishikawa, S.; Manabe,
K. Chem. Commun. 2006, 2589; (c) Manabe, K.; Ishikawa, S. Chem. Commun.
2008, 3829.
J¼7.6 Hz), 6.94 (1H, d, J¼7.6 Hz), 7.15–7.28 (3H, m), 7.20 (2H, d,
J¼8.0 Hz), 7.41–7.50 (2H, m), 7.49 (2H, d, J¼8.0 Hz), 7.67 (1H, dd,
J¼7.6, 10.8 Hz) ppm; 13C NMR (100 MHz, CDCl3/CD3OD¼10/1)
d
25.52, 25.53, 25.86 (d, J¼3.3 Hz), 26.20 (d, J¼11.5 Hz), 26.25 (d,
J¼11.5 Hz), 37.30 (d, J¼67.7 Hz), 116.46, 119.77, 126.94 (d,
J¼9.8 Hz), 127.88 (d, J¼82.6 Hz), 128.12, 128.37, 128.70, 130.23,
130.69, 131.62 (d, J¼8.2 Hz), 131.74 (d, J¼8.2 Hz), 137.78, 139.92,
139.94, 146.17 (d, J¼6.6 Hz), 153.91 ppm; 31P NMR (202 MHz,
CDCl3/CD3OD¼10/1)
d 51.43 ppm; IR (ATR) 3064, 2931, 2854, 1446,
1132, 750 cmꢁ1; HRMS (ESI) m/z calcd for C30H34O2P ([MꢁH]ꢁ)
457.2302; found: 457.2305; Anal. Calcd for C30H35O2P: C, 78.57; H,
7.69, found: C, 78.55; H, 7.72%.
4.5. Compound 52: reduction of 28 and salt formation
with HBF4
6. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
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Prock, A.; Giering, W. P. Organometallics 1989, 8, 1.
8. The use of a PCy2 group in biaryl-type phosphines: Surry, D. S.; Buchwald, S. L.
Angew. Chem., Int. Ed. 2008, 47, 6338. And references therein.
9. An example of chemoselective cross-coupling between OTf and Cl: Littke, A. F.;
Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2000, 122, 4020.
10. Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12051.
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12. Murata, M.; Buchwald, S. L. Tetrahedron 2004, 60, 7397.
13. Lappert, M. F. Chem. Rev. 1956, 56, 959.
14. (a) Guijarro, A.; Ramo´n, D. J.; Yus, M. Tetrahedron 1993, 49, 469; (b) Alonso, F.;
Lorenzo, E.; Yus, M. J. Org. Chem.1996, 61, 6058; (c) Huerta, F. F.; Go´mez, C.; Yus, M.
To a toluene (10.0 mL) suspension of 28 (306 mg, 0.668 mmol)
in a sealed tube filled with argon were added NEt3 (2.79 mL,
20.0 mmol) and HSiCl3 (1.01 mL, 10.0 mmol) at ꢁ78 ꢀC, and the
whole was then stirred at 0 ꢀC for 30 min, then at 110 ꢀC for 24 h.
After cooling to rt, a saturated aqueous NaHCO3 solution and MeOH
were added, and the mixture was filtered through Celite and
washed with EtOAc and MeOH. The phases were separated and the
organic layer was washed with brine, dried over Na2SO4, and
concentrated. Purification by column chromatography (silica gel,
EtOAc/hexane¼1/5) gave the reduced product. The product was
then dissolved in CH2Cl2 (7.92 mL), and to the solution was added
HBF4 aqueous solution (42 wt %, 0.56 mL). The whole was stirred
at rt for 15 min, and then diluted with CH2Cl2. The phases were
separated and the organic layer was dried over MgSO4 and con-
centrated. Recrystallization from hexane/CH2Cl2 gave colorless
block containing CH2Cl2 molecules. The blocks were dissolved in
MeOH, then concentrated, and dried in vacuo at 100 ꢀC. The desired
product 52 was obtained as a white solid in 49% yield (174 mg). Mp
´
Tetrahedron 1999, 55, 4043; (d) Ramon, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225.
15. Heinicke, J.; Ko¨hler, M.; Peulecke, N.; He, M.; Kindermann, M. K.; Keim, W.;
Fink, G. Chem.dEur. J. 2003, 9, 6093.
16. Wolfe, J. P.; Buchwald, S. L. Angew. Chem., Int. Ed. 1999, 38, 2413.
17. Barder, T. E.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 5096.
18. Gilman, H.; Santucci, L.; Swayampati, D. R.; Ranck, R. O. J. Am. Chem. Soc. 1957,
79, 3077. The real aggregation states of the boronic anhydrides are unclear
because of the complexity associated with the phenolic hydroxy groups.
19. Reid, S. M.; Boyle, R. C.; Mague, J. T.; Fink, M. J. J. Am. Chem. Soc. 2003, 125, 7816.
20. (a) Hendrickson, J. B.; Bergeron, R. Tetrahedron Lett. 1973, 14, 4607. Examples of
the use of PhNTf2 for the triflation of phenol in the presence of phosphine
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111.4–138.7 ꢀC; 1H NMR (400 MHz, CD3OD)
d 1.18–1.47 (10H, m),
1.70–1.89 (10H, m), 2.72–2.81 (2H, m), 6.91–6.95 (2H, m), 7.20 (1H,
dt, J¼1.2, 7.6 Hz), 7.33 (2H, d, J¼8.2 Hz), 7.32–7.34 (1H, m), 7.65 (1H,
dd, J¼4.6, 7.6 Hz), 7.75 (2H, d, J¼8.2 Hz), 7.74–7.78 (1H, m), 7.89
(1H, t, J¼7.6 Hz), 7.99 (1H, dd, J¼7.6, 12.2 Hz) ppm; 13C NMR
(100 MHz, CD3OD)
d
26.16, 26.78 (d, J¼14.9 Hz), 26.78 (d,
24. Naumann, K.; Zon, G.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7012.
25. Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3, 4295.
26. A repetitive strategy using methoxy group to synthesize oligoaryl structure had
been reported: Ernst, J. T.; Kutzki, O.; Debnath, A. K.; Jiang, S.; Lu, H.; Hamilton,
A. D. Angew. Chem., Int. Ed. 2002, 41, 278. See also Ref. 5a.
J¼14.9 Hz), 27.76 (d, J¼3.3 Hz), 28.63, 30.33 (d, J¼41.1 Hz), 116.97,
121.12, 128.56, 130.07 (d, J¼13.2 Hz), 130.19, 130.30, 131.12, 131.55,
133.25 (d, J¼8.2 Hz), 134.61 (d, J¼9.9 Hz), 135.75, 137.94 (d,
J¼4.9 Hz), 141.41, 150.51 (d, J¼6.6 Hz), 155.51 ppm (one carbon
27. Torraca, K. E.; Kuwabe, S.-I.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12907.