M. Shimizu et al. / Tetrahedron 67 (2011) 8014e8026
8025
m/z: 454 (7, Mþþ2), 453 (36, Mþþ1), 452 (100, Mþ), 422 (3). Anal.
Sports, Science and Technology, Japan, and The Asahi Glass
Foundation.
Calcd for C31H23F3: C, 82.28; H, 5.12. Found: C, 82.20; H, 5.08.
4.7.6. 4,5,6,7,8,9,10,11-Octafluorotriphenyleno[1,2-b:4,3-b0]dithio-
phene (4gh). Purified by recrystallization from MeOH. Yield: 81%,
colorless solid. Mp: 241.1e241.4 ꢀC. TLC: Rf 0.30 (hexane/AcOEt/
References and notes
1. Reviews on PAHs for organic electronics: (a) Weil, T.; Vosch, T.; Hofkens, J.; Peneva,
€
K.; Mullen, K. Angew. Chem., Int. Ed. 2010, 49, 9068e9093; (b) Avlasevich, Y.; Li, C.;
CH2Cl2 40:1:1). 1H NMR (400 MHz, CDCl3):
d
7.81 (s, 4H); 19F NMR
€
Mullen, K. J. Mater. Chem. 2010, 20, 3814e3826; (c) Wu, J.; Pisula, W.; Mullen, K.
(282 MHz, CDCl3):
d
ꢁ155.6 to ꢁ155.2 (m, 2F), ꢁ153.2 to ꢁ152.8 (t,
ꢀ
Chem. Rev. 2007, 107, 718e747; (d) Murphy, A. R.; Frechet, J. M. J. Chem. Rev. 2007,
107, 1066e1096; (e) Grimsdale, A. C.; Mullen, K. Macromol. Rapid Commun. 2007,
28, 1676e1702; (f) Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36,
1902e1929; (g) Anthony, J. E. Chem. Rev. 2006, 106, 5028e5048; (h) Bendikov, M.;
Wudl, F.; Perepichka, D. F. Chem. Rev. 2004, 104, 4891e4945; (i) Watson, M. D.;
€
J¼6.5 Hz, 2F), ꢁ129.8 (br s, 2F), ꢁ123.9 (d, J¼8.6 Hz, 2F). IR (KBr):
n
¼1518, 1481, 1074, 964, 723 cmꢁ1. MS (EI) m/z: 486 (12, Mþþ2),
485 (25, Mþþ1), 484 (100 Mþ). Anal. Calcd for C22H4F8S2: C, 54.55;
€
€
Fechtenkotter, A.; Mullen, K. Chem. Rev. 2001,101,1267e1300; (j) Berresheim, A. J.;
H, 0.83. Found: C, 54.31; H, 0.90.
€
€
Muller, M.; Mullen, K. Chem. Rev. 1999, 99, 1747e1786.
2. Smith, M. B.; March, J. In Advanced Organic Chemistry; John Wiley: New York,
NY, 2001; pp 675e758; and 850e893.
3. (a) Metal-catalyzed Cross-coupling Reactions; Diederich, F., Stang, P. J., Eds.;
Wiley-VCH: Weinheim, 1998; (b) Top. Curr. Chem.; Miyaura, N., Ed.; Springer:
Berlin, 2002; (c) Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A., Die-
derich, F., Eds.; Wiley-VCH: Weinheim, 2004.
4. (a) Snieckus, V. Chem. Rev. 1990, 90, 879e933; (b) Hartung, C. G.; Snieckus, V. In
Modern Arene Chemistry; Astruc, D., Ed.; Wiley-VCH: Weinheim, 2002;
pp 330e367; (c) Mulvey, R. E.; Mongin, F.; Uchiyama, M.; Kondo, Y. Angew.
Chem., Int. Ed. 2007, 46, 3802e3824.
5. (a) Xue, X.; Scott, L. T. Org. Lett. 2007, 9, 3937e3940; (b) Shimizu, M.; Tomioka,
Y.; Nagao, I.; Hiyama, T. Synlett 2009, 3147e3150.
6. Goodby, J. W.; Hird, M.; Toyne, K. J.; Watson, T. J. Chem. Soc., Chem. Commun.
1994, 1701e1702.
7. (a) Takahashi, T.; Hara, R.; Nishihara, Y.; Kotora, M. J. Am. Chem. Soc. 1996, 118,
5154e5155; (b) Takahashi, T.; Li, Y.; Stepnicka, P.; Kitamura, M.; Liu, Y.; Naka-
jima, K.; Kotora, M. J. Am. Chem. Soc. 2002, 124, 576e582.
4.7.7. 1,2,3,4,5,6,7,8-Octafluorotriphenylene (4hh). Purified by silica
gel column chromatography (hexane). Yield: 85%, colorless solid.
Mp: 163.5e164.3 ꢀC. TLC: Rf 0.43 (hexane/AcOEt 40:1). 1H NMR
(400 MHz, CDCl3):
CDCl3):
d
7.73 (m, 2H), 8.86 (m, 2H); 13C NMR (100 MHz,
d
110.1, 116.5, 126.3, 127.1 (d, J¼26.7 Hz), 129.2, 139.6 (d,
J¼261.5 Hz), 140.8 (ddd, J¼252.4, 31.2, 13.0 Hz), 144.4 (dd, J¼254.7,
9.9 Hz), 145.2 (dd, J¼249.3, 12.2 Hz); 19F NMR (282 MHz, CDCl3):
d
ꢁ156.2, ꢁ154.3 to ꢁ154.2 (m), ꢁ138.9, ꢁ130.2. IR (KBr): ¼1636,
n
1613, 1597, 1518, 1476, 1435, 1364, 1335, 1092, 1084, 1034, 951, 883,
821, 772, 723, 654 cmꢁ1. MS (EI) m/z: 374 (2, Mþþ2), 373 (20,
Mþþ1), 372 (100, Mþ). Anal. Calcd for C18H4F8: C, 58.08; H, 1.08.
Found: C, 58.04; H, 1.22.
8. Hilton, C. L.; Jamison, C. R.; King, B. T. J. Am. Chem. Soc. 2006, 128, 14824.
9. Nagao, I.; Shimizu, M.; Hiyama, T. Angew. Chem., Int. Ed. 2009, 48, 7573e7576.
10. Recently palladium-catalyzed double cross-coupling reaction of 1,2-
bis(pinacolatoboryl)benzene and 1,8-dihalonaphthalenes was reported, which
could be regarded as annulation between 1,2-dimetal reagents and 1,3-dihalides.
Yoshida, H.; Okada, K.; Kawashima, S.; Tanino, K.; Ohshita, J. Chem. Commun. 2010,
1763e1765.
11. Reviews on polyborylated reagents in organic synthesis: (a) Dembitsky, V. M.;
Ali, H. A.; Srebnik, M. Appl. Organomet. Chem. 2003, 17, 327e345; (b) Shimizu,
M.; Hiyama, T. Proc. Jpn. Acad., Ser. B 2008, 84, 75e85.
12. (a) Marder, T. B.; Norman, N. C. Top. Catal. 1998, 5, 63e73; (b) Ishiyama, T.;
Miyaura, N. J. Organomet. Chem. 2000, 611, 392e402; (c) Ishiyama, T.; Miyaura,
N. Chem. Rec. 2004, 3, 271e280; (d) Burks, H. E.; Morken, J. P. Chem. Commun.
2007, 4717e4725; (e) Ishiyama, T.; Matsuda, N.; Miyaura, N.; Suzuki, A. J. Am.
Chem. Soc. 1993, 115, 11018e11019; (f) Ishiyama, T.; Matsuda, N.; Murata, M.;
Ozawa, F.; Suzuki, A.; Miyaura, N. Organometallics 1996, 15, 713e720.
13. Reviews on SuzukieMiyaura coupling reaction: (a) Miyaura, N.; Suzuki, A. Chem.
Rev.1995, 95, 2457e2483; (b) Suzuki, A. In Metal-catalyzed Cross-coupling Reactions;
Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim,1998; pp 49e97; (c) Miyaura,
N. In Cross-Coupling Reaction: A Practical Guide; Miyaura, N., Ed.; Springer: Berlin,
2002; pp 11e59; (d) Miyaura, N. In Metal-Catalyzed Cross-Coupling Reactions; de
Meijere, A., Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004; pp 41e123.
14. Shimizu, M.; Nagao, I.; Tomioka, Y.; Hiyama, T. Angew. Chem., Int. Ed. 2008, 47,
8096e8099.
4.7.8. 1,2,3,4,5,6,7,8-Octafluoro-10,11-dimethoxytriphenylene
(4ih). Purified by silica gel column chromatography (hexane/AcOEt
20:1). Yield: 42%, colorless solid. Mp: 225.2e226.3 ꢀC. TLC: Rf 0.13
(hexane/AcOEt 20:1). 1H NMR (400 MHz, CDCl3):
d
4.09 (s, 6H), 8.34
55.9, 108.4 (d,
(JHeF¼5.2 Hz); 13C NMR (100 MHz, CDCl3):
d
J¼27.5 Hz), 109.7, 116.5, 120.9, 139.0 (d, J¼250.8 Hz), 140.7 (ddd,
J¼251.6,16.0,13.0 Hz),144.5 (dd, J¼248.6,13 Hz),144.4 (dd, J¼209.7,
130.4); 19F NMR (282 MHz, CDCl3):
d
ꢁ157.8 to ꢁ157.7 (m), ꢁ155.0
to ꢁ154.8 (m), ꢁ141.1, ꢁ130.0. IR (KBr): ¼1609, 1533, 1520, 1466,
n
1420, 1370, 1283, 1219, 1146, 1082, 1071, 851, 721 cmꢁ1. MS (EI) m/z:
434 (3, Mþþ2), 433 (24, Mþþ1), 432 (100, Mþ). Anal. Calcd for
C20H8F8O2: C, 55.57; H, 1.87. Found: C, 55.49; H, 1.97.
4.7.9. 1,2,3,4,5,6,7,8-Octafluoro-10,11-dimethyltriphenylene
(4jh). Purified bysilica gel column chromatography (hexane). Yield:
76%, colorless solid. Mp: 210.4e211.6 ꢀC. TLC: Rf 0.36 (hexane/AcOEt
40:1). 1H NMR (400 MHz, CDCl3):
13C NMR (100 MHz, CDCl3):
d
2.51 (s, 6H), 8.62 (JHeF¼1.6 Hz);
d
20.5, 109.9, 116.6, 124.3, 127.6 (d,
15. Mallory, F. B.; Mallory, C. W. Org. React. 1984, 30, 1e456.
J¼25.9 Hz), 138.5, 139.1 (d, J¼260.7 Hz), 140.7 (ddd, J¼251.6, 18.3,
16. Liu, L.; Yang, B.; Katz, T. J.; Poindexter, M. K. J. Org. Chem. 1991, 56, 3769e3775.
17. Billingsley, K. L.; Buchwald, S. L. J. Org. Chem. 2008, 73, 5589e5591.
18. Precedents of the preparation of 1,2-diborylbenzenes: (a) Shimizu, M.; Shi-
mono, K.; Kurahashi, T.; Kiyomoto, S.-i.; Nagao, I.; Hiyama, T. Bull. Chem. Soc.
Jpn. 2008, 81, 518e520; (b) Noguchi, H.; Shioda, T.; Chou, C. M.; Suginome, M.
Org. Lett. 2008, 10, 377e380; (c) Nozaki, K.; Yoshida, M.; Takaya, H. Bull. Chem.
Soc. Jpn. 1996, 69, 2043e2052; (d) Nozaki, K.; Yoshida, M.; Takaya, H. Angew.
Chem., Int. Ed. Engl. 1995, 33, 2452e2454; (e) Ref. 10.
12.9 Hz),144.4 (d, J¼263.1 Hz),144.8 (dd, J¼250.8,10.7 Hz); 19F NMR
(282 MHz, CDCl3):
d
ꢁ157.4, ꢁ155.0 to ꢁ154.8 (m), ꢁ139.3, ꢁ130.6. IR
(KBr):
n
¼1638, 1611, 1520, 1481, 1474, 1443, 1072, 718 cmꢁ1. MS (EI)
m/z: 402 (3, Mþþ2), 401 (23, Mþþ1), 400 (100, Mþ). Anal. Calcd for
C20H8F8: C, 60.01; H, 2.01. Found: C, 59.84; H, 1.97.
19. The acceleration of SuzukieMiyaura coupling by the addition of H2O was ob-
served in some cases. (a) Miyaura, N. Top. Curr. Chem. 2002, 219, 20e23; (b)
Johnson, C. R.; Braun, M. P. J. Am. Chem. Soc. 1993, 115, 11014e11015; (c) Zhou, C.;
Emrich, D. E.; Larock, R. C. Org. Lett. 2003, 5, 1579e1582; (d) Liu, X.; Shimizu, M.;
Hiyama, T. Angew. Chem., Int. Ed. 2004, 43, 879e882; (e) Barder, T. E.; Walker, S.
D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685e4696; (f)
Zhou, C.; Larock, R. C. J. Org. Chem. 2005, 70, 3765e3777.
4.7.10. Naphtho[1,2-b:4,3-b0]dithiophene (4hj). Purified by silica gel
column chromatography (hexane). Yield: 37%, colorless solid. Mp:
172.0e172.8 ꢀC. TLC: Rf 0.28 (hexane/AcOEt 40:1). 1H NMR
(400 MHz, CDCl3):
d
7.58 (dd, J¼6.4, 3.2 Hz, 2H), 7.59 (d, J¼5.2 Hz,
2H), 7.76 (d, J¼5.2 Hz, 2H), 8.19 (dd, J¼6.4, 3.2 Hz, 2H); 13C NMR
20. Both more diluted (0.005 M) and concentrated (0.5 M) conditions than 0.05 M
(100 MHz, CDCl3): d 122.9, 124.4, 125.3, 126.2, 126.8, 133.2, 135.3. IR
were much less effective (4% and 7% GC yields, respectively).
(KBr):
n
¼1456, 1400, 1258, 1098, 845, 752, 748, 625, 617 cmꢁ1. MS
21. Examples of palladium-catalyzed synthesis of 9,10-diarylphenanthrenes: (a)
Dyker, G. J. Org. Chem. 1993, 58, 234e238; (b) Dyker, G.; Kellner, A. Tetrahedron
Lett. 1994, 35, 7633e7636; (c) Larock, R. C.; Doty, M. J.; Tian, Q.; Zenner, J. M. J.
Org. Chem. 1997, 62, 7536e7537; (d) Tian, Q.; Larock, R. C. Org. Lett. 2000, 2,
3329e3332; (e) Larock, R. C.; Tian, Q. J. Org. Chem. 2001, 66, 7372e7379; (f) Liu,
Z.; Larock, R. C. J. Org. Chem. 2007, 72, 223e232; (g) Wang, C.; Rakshit, S.;
Glorius, F. J. Am. Chem. Soc. 2010, 132, 14006e14008.
22. Previous syntheses of dithienobenzenes: (a) Archer, W. J.; Cook, R.; Taylor, R. J.
Chem. Soc., Perkin Trans. 2 1983, 813e819; (b) Yoshida, S.; Fujii, M.; Aso, Y.;
Otsubo, T.; Ogura, F. J. Org. Chem. 1994, 59, 3077e3081; (c) Dahlmann, U.;
Neidlein, R. Helv. Chim. Acta 1997, 80, 111e120; (d) Imamura, K.; Hirayama, D.;
(EI) m/z: 243 (2, Mþþ3), 242 (11, Mþþ2), 241 (20, Mþþ1), 240 (100,
Mþ). Anal. Calcd for C14H8S2: C, 69.96; H, 3.36. Found: C, 70.01; H,
3.44.
Acknowledgements
This work was supported by Grants-in-Aid for Creative Scientific
Research, No. 16GS0209 from the Ministry of Education, Culture,