6
Tetrahedron
ACCEPTED MANUSCRIPT
ppm; 13C NMR (100 MHz, CDCl3): δ 140.38, 134.64, 127.35,
ChemSusChem. 2012, 5, 22; f) Alonso, D. A.; Nájera, C. Chem.
Soc. Rev. 2010, 39, 2891.
124.58 ppm.
2. a) Campelo, J. M.; Luna, D.; Luque, R.; Marinas, J. M.; Romero,
A. A. ChemSusChem. 2009, 2, 18; b) Yin, L.; Liebscher, J. Chem.
Rev. 2007, 107, 133.
4.3.15 1,1′-Binaphthyl (4o). White solid; M.p. = 156-157 oC; Rf =
0.6 (Petroleum ether); H NMR (600 MHz, CDCl3): δ = 7.26-
7.29 (m, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.44-7.50 (m, 4H), 7.58 (t,
J = 7.0 Hz, 2H), 7.95 (dd, J = 5.6, 8.2 Hz, 4H) ppm; 13C NMR
(100 MHz, CDCl3): δ 138.48, 133.54, 132.87, 128.17, 127.91,
127.85, 126.58, 126.00, 125.83, 125.40 ppm.
1
3. a) Mori, K.; Yamaguchi, K.; Hara, T.; Mizugaki, T.; Ebitani, K.;
Kaneda, K. J. Am. Chem. Soc. 2002, 124, 11572; b) Gniewek, A.;
Ziółkowski, J.; Trzeciak, A. M.; Zawadzki, M.; Grabowska, H.;
Wrzyszcz, J. J. Catal. 2008, 254, 121; c) Primo, A.; Quignard, F.
Chem. Commun. 2010, 46, 5593; d) Choudary, B. M.; Madhi, S.;
Chowdari, N. S.; Kantam, M. L.; Sreedhar, B. J. Am. Chem. Soc.
2002, 124, 14127; e) Narayanan, R.; El-Sayed, M. A. J. Am.
Chem. Soc. 2003, 125, 8340.
4.3.16 2,2′-Binaphthyl (4p). White solid; M.p. = 156-157 oC; Rf =
0.6 (Petroleum ether); H NMR (600 MHz, CDCl3): δ = 7.48-
1
4. a) Moreno-Maňas, M.; Pleixats, R. Acc. Chem. Res. 2003, 36, 638;
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Chem. Int. Ed. 2005, 44, 7852.
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Liu, J.; Lam, J. W.; Tang, B. Z. Chem. Rev. 2009, 109, 5799; c)
Gleiter, R.; Werz, D. B. Chem. Rev. 2010, 110, 4447; d) Gleiter,
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Angew. Chem. Int. Ed. 2006, 45, 1034.
6. For reviews, See: a) Siemsen, P.; Livingston, R. C.; Diederich, F.
Angew. Chem. Int. Ed. 2000, 39, 2632; b) Stefani, H. A.;
Guarezemini, A. S.; Cella, R. Tetrahedron 2010, 66, 7871; c) Bai,
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7. a) Chen, L.; Lemma, B. E.; Rich, J. S.; Mack, J. Green Chem.
2014, 16, 1101; b) Li, J. H.; Liang, Y.; Zhang, X. D. Tetrahedron
2005, 61, 1903; c) Yang, F.; Cui, X.; Li, Y. N.; Zhang, J.; Ren, G.
R.; Wu, Y. Tetrahedron 2007, 63, 1963; d) Oh, C. H.; Reddy, V.
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Synthesis 2007, 1301; f) Chen, S. N.; Wu, W. Y.; Tsai, F. Y.
Green Chem. 2009, 11, 269; g) Fairlamb, I. J. S.; Bäuerlein, P. S.;
Marrison, L. R.; Dickinson, J. M. Chem. Commun. 2003, 632; h)
Li, J. H.; Liang, Y.; Xie, Y. X. J. Org. Chem. 2005, 70, 4393; i)
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7.53 (m, 4H), 7.87 (d, J = 1.9 Hz, 2H), 7.89 (d, J = 1.8 Hz, 2H),
7.93 (d, J = 7.9 Hz, 2H), 7.96 (d, J = 8.4 Hz, 2H), 8.17 (d, J = 1.0
Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 132.69, 128.55,
128.26, 127.70, 126.38, 126.14, 126.03, 125.76 ppm.
o
4.3.17 3,3'-Bithiophenyl (4q).White solid; M.p. = 126-127 C; Rf
1
= 0.6 (Petroleum ether); H NMR (600 MHz, CDCl3): δ = 7.32-
7.36 (m, 4H), 7.37-7.39 (m, 2H) ppm; 13C NMR (100 MHz,
CDCl3): δ 137.26, 126.38, 126.11, 119.81 ppm; HRMS (ESI):
Calcd for C8H6S2+H 166.9989, found 166.9985.
o
4.3.18 4,4'-Bipyridyl (4r). White solid; M.p. = 111-112 C; Rf =
0.3 (Petroleum ether/Ethyl acetate = 2/1 v/v); 1H NMR (400 MHz,
CDCl3): δ = 7.55 (dd, J = 1.6, 4.5 Hz, 4H), 8.76 (d, J = 5.7 Hz,
4H) ppm; 13C NMR (100 MHz, CDCl3): δ 150.63, 145.50, 121.40
ppm; HR-MS (ESI): Calcd for C10H8N2+H 157.0766, found
157.0755.
4.4.Typical experimental procedure for homocoupling of
potassium aryltrifluoroborates
A mixture of potassium aryltrifluoroborate 5 (0.2 mmol),
nano-Pd (0.1 mol% Pd), Ag2O (45 mol%), KOAc (1 equiv), and
H2O (0.8 mL) was stirred at specified temperature until complete
consumption of starting material as determined by TLC. After the
mixture was filtered and evaporated, the residue was purified by
flash column chromatography to afford the corresponding
8. a) Bedard, A. C.; Collins, S. K. J. Am. Chem. Soc. 2011, 133,
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6243.
homocoupling product
ether/ethylacetate).
4 (petroleum ether or petroleum
9. For recent selected examples, see: a) He, Y.; Cai, C. Catal. Sci.
Technol. 2012, 2, 1126; b) Suárez, J. R.; Collado-Sanz, D.;
Cárdenas, D. J.; Chiara, J. L. J. Org. Chem. 2015, 80, 1098; c)
Xiao, R.; Yao, R.; Cai, M. Eur. J. Org. Chem. 2012, 4178; d)
Adimurthy, S.; Malakar, C.; Beifuss, U. J. Org. Chem. 2009, 74,
5648; e) Niu, X.; Li, C.; Li, J.; Jia, X. Tetrahedron Lett. 2012, 53,
5559; f) Oishi, T.; Yamaguchi, K.; Mizuno, N. ACS Catal. 2011,
1, 1351; g) Schmidt, R.; Thorwirth, R.; Szuppa, T.; Stolle, A.;
Ondruschka, B.; Hopf, H. Chem. Eur. J. 2011, 17, 8129; h)
Kusuda, A.; Xu, X. H.; Wang, X.; Tokunaga, E.; Shibata, N.
Green Chem. 2011, 13, 843; i) Kamata, K.; Yamaguchi, S.;
Kotani, M.; Yamaguchi, K.; Mizuno, N. Angew. Chem., Int. Ed.
2008, 47, 2407; j) Liao, Y.; Fathi, R.; Yang, Z. Org. Lett. 2003, 5,
909; k) Zhang, S.; Liu, X.; Wang, T. Adv. Synth. Catal. 2011, 353,
1463; l) Yin, K.; Li, C.; Li, J.; Jia, X. Green Chem. 2011, 13, 591;
m) Wang, D.; Li, J.; Li, N.; Gao, T.; Hou, S.; Chen, B. Green
Chem. 2010, 12, 45; n) Ren, Y.; Li, M.; Yang, J.; Peng, J.; Gu, Y.
Adv. Synth. Catal. 2011, 353, 3473; o) Sun, Q.; Lv, Z.; Du, Y.;
Wu, Q.; Wang, L.; Zhu, L.; Meng, X.; Chen, W.; Xiao, F. S.
Chem. Asian J. 2013, 8, 2822; p) Alonso, F.; Melkonian, T.;
Moglie, Y.; Yus, M. Eur. J. Org. Chem. 2011, 2524; q) Li, Y. N.;
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J. Org. Chem. 2009, 423; s) Balaraman, K.; Venkitasamy, K.
Synthesis 2010, 3461.
4.4.1 4,4'-Difluorobiphenyl (4s). White solid; M.p. = 88-91 oC; Rf
1
= 0.6 (Petroleum ether); H NMR (400 MHz, CDCl3): δ = 7.08-
7.15 (m, 4H), 7.45-7.51 (m, 4H) ppm; 13C NMR (100 MHz,
CDCl3): δ 128.63, 128.55, 115.80, 115.59 ppm.
4.4.2 3,3'-Difluorobiphenyl (4t). Colorless oil; Rf
= 0.6
1
(Petroleum ether); H NMR (400 MHz, CDCl3): δ = 7.09 (tdd, J
= 1.0, 2.6, 8.4 Hz, 2H), 7.25 (t, J = 1.8 Hz, 1H), 7.28 (t, J = 2.3
Hz, 1H), 7.34 (t, J = 1.4 Hz, 1H), 7.36 (t, J = 1.4 Hz, 1H), 7.38-
7.44 (m, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 130.44 (d, J
= 8.5 Hz) 122.76 (d, J = 2.8 Hz) 114.77, 114.56, 114.16, 113.94
ppm; HR-MS (ESI): Calcd for C12H8F2+H 191.0672, found
191.0675.
Acknowledgments
We appreciate gratefully the Natural Science Foundation of
Shanxi Province (No. 201601D011028) for financial support.
References and notes
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