4
Tetrahedron
ACCEPTED MANUSCRIPT
J = 8.5 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ 162.8 (d, JC-F
=
162.3 (d, JC-F = 245.875 Hz), 143.6, 142.4, 134.2, 130.6 (d, JC-F =
246.875 Hz), 143.1, 140.7, 139.5, 130.6 (d, JC-F = 3.375 Hz),
128.2 (d, JC-F = 8.125 Hz), 124.6, 124.4, 123.5, 122.2, 119.4,
115.9 (d, JC-F = 21.75 Hz).
3.375 Hz), 128.9, 127.6, 127.3 (d, JC-F = 8.0 Hz), 125.6, 124.0,
116.9 (d, JC-F = 21.75 Hz). IR (neat) ν 2346, 1590, 1540, 1511,
1494, 1455, 1238, 1159, 1101, 937, 906, 864, 835, 801, 755 cm-1.
MS (ESI): 255 [M+H]+; HRMS (ESI) calcd for C16H12FS
[M+H]+: 255.0638; found: 255.0647.
1
4.2.9 Compound 4i2j: white solid. H NMR (CDCl3, 500 MHz,
TMS) δ 7.64 (d, J = 7.5 Hz, 4H), 7.40 (t, J = 7.5 Hz, 4H), 7.30-
7.27 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 143.6, 134.3, 128.9,
127.5, 125.6, 124.0.
1
4.2.17 Compound 4q5: colorless liquid. H NMR (CDCl3, 500
MHz, TMS) δ 7.34 (d, J = 9.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 1H),
7.07 (d, J = 4.0 Hz, 1H), 7.03 (d, J = 7.5 Hz, 1H), 6.69-6.68 (m,
1H), 2.48 (s, 3H), 2.35 (s, 3H). 13C NMR (CDCl3, 125 MHz) δ
142.1, 139.2, 138.3, 134.6, 128.7, 127.8, 126.2, 126.1, 122.7,
122.6, 21.4, 15.4.
1
4.2.10 Compound 4j2b: white solid. H NMR (CDCl3, 500 MHz,
TMS) δ 7.63 (d, J = 7.5 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H), 7.39 (t,
J = 8.0 Hz, 2H), 7.29-7.24 (m, 3H), 7.20 (d, J = 8.0 Hz, 1H), 2.37
(s, 3H). 13C NMR (CDCl3, 125 MHz) δ 143.8, 143.0, 137.4,
134.4, 131.5, 129.6, 128.9, 127.4, 125.6, 125.5, 123.9, 123.5,
21.2.
4.2.18 Compound 4r2a: white solid. H NMR (CDCl3, 500 MHz,
1
TMS) δ 7.43 (d, J = 8.5 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 7.04
(d, J = 3.5 Hz, 1H), 6.69-6.68 (m, 1H), 2.48 (s, 3H), 2.33 (s, 3H).
13C NMR (CDCl3, 125 MHz) δ 142.1, 138.8, 136.7, 131.9, 129.4,
126.0, 125.4, 122.3, 21.1, 15.4.
1
4.2.11 Compound 4k11: white solid. H NMR (CDCl3, 500 MHz,
TMS) δ 7.64 (d, J = 8.0 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 (t,
J = 7.5 Hz, 2H), 7.30-7.27 (m, 4H), 7.11 (d, J = 8.0 Hz, 1H), 2.40
(s, 3H). 13C NMR (CDCl3, 125 MHz) δ 143.8, 143.4, 138.5,
134.3, 134.2, 128.9, 128.8, 128.3, 127.4, 126.3, 125.6, 123.9,
123.8, 122.7, 21.4.
1
4.2.19 Compound 4s2a: colorless liquid. H NMR (CDCl3, 500
MHz, TMS) δ 7.38-7.36 (m, 1H), 7.24-7.16 (m, 3H), 6.84 (d, J
= 3.0 Hz, 1H), 6.73-6.72 (m, 1H), 2.50 (s, 3H), 2.42 (s, 3H). 13
C
NMR (CDCl3, 125 MHz) δ 140.8, 139.6, 135.9, 134.5, 130.7,
130.2, 127.4, 126.2, 125.8, 125.3, 21.2, 15.2.
1
4.2.12 Compound 4l11: white solid. H NMR (CDCl3, 500 MHz,
TMS) δ 7.63 (d, J = 8.0 Hz, 2H), 7.46-7.44 (m, 1H), 7.39 (t, J =
7.5 Hz, 2H), 7.30-7.22 (m, 5H), 7.04 (d, J = 3.5 Hz, 1H), 2.49 (s,
3H). 13C NMR (CDCl3, 125 MHz) δ 143.9, 142.5, 135.9, 134.3,
134.0, 130.8, 130.2, 128.9, 127.8, 127.4, 126.0, 125.6, 123.1,
21.2.
4.2.20 Compound 4t2a: yellow solid. 1H NMR (CDCl3, 500 MHz,
TMS) δ 7.47-7.44 (m, 2H), 6.97 (d, J = 3.5 Hz, 1H), 6.89-6.86
(m, 2H), 6.68-6.67 (m, 1H), 3.80 (s, 3H), 2.48 (s, 3H). 13C NMR
(CDCl3, 125 MHz) δ 158.8, 141.9, 138.4, 127.6, 126.7, 126.0,
121.8, 114.2, 55.3, 15.3.
4.2.13 Compound 4m2f: yellow solid. 1H NMR (CDCl3, 500
MHz, TMS) δ 7.62 (d, J = 7.5 Hz, 2H), 7.56 (d, J = 8.0 Hz, 2H),
7.38 (t, J = 7.5 Hz, 2H), 7.28-7.25 (m, 2H), 7.17 (s, 1H), 6.92 (d,
J = 8.0 Hz, 2H), 3.84 (s, 3H). 13C NMR (CDCl3, 125 MHz) δ
159.2, 143.6, 142.6, 134.4, 128.9, 127.3, 127.2, 126.9, 125.5,
123.9, 122.9, 114.3, 55.4.
Acknowledgments
Quan Zhou thanks the University Students’ Innovative
Undertaking Training Program for financial support. Peng-Cheng
Qian thanks the Financial support from the Foundation of
Department of Education, Zhejiang Province (No. Y201327597)
and Natural Science Foundation of Zhejiang Province (No.
LY15B020002).
4.2.14 Compound 4n12: yellow solid. 1H NMR (CDCl3, 500
MHz, TMS) δ 7.62 (d, J = 7.0 Hz, 2H), 7.38 (t, J = 7.0 Hz, 2H),
7.31-7.23 (m, 5H), 7.16 (s, 1H), 6.83 (d, J = 8.0 Hz, 1H), 3.84 (s,
3H). 13C NMR (CDCl3, 125 MHz) δ 159.9, 143.7, 143.4, 135.6,
134.2, 129.9, 128.9, 127.5, 125.6, 124.2, 123.9, 118.2, 113.0,
111.2, 55.3.
References and notes
1. For some recent reviews on the direct C-H bond functionalization
of heteroaromatic compounds, please see: (a) Sharma, U.; Modak,
A.; Maity, S.; Maji, A.; Maiti, D. Direct arylation via C-H
activation, in New Trends in Cross-Coupling: Theory and
Applications; Ed.: Colacot, T.; RSC Catalysis Series: The Royal
Society of Chemistry, 2015, pp551-609. (b) Yamaguchi, J.; Itami,
K. Biaryl synthesis through metal-catalyzed C-H arylation, in
Metal-Catalyzed Cross-Coupling Reactions and More; Eds.: de
Meijre, A.; Bräse, S.; Oestreich, M.; Wiley-VCH Verlag GmbH &
Co. KGaA; 2014, Volumn 3, Chapter 17, pp1315-1387. (c) Rossi,
R.; Bellina, F.; Lessi, M.; Manzini, C. Adv. Synth. Catal. 2014,
356, 17-117. (d) Bonin, H.; Sauthier, M.; Felpin, F.-X. Adv. Synth.
Catal. 2014, 356, 645-671. (e) Daugulis, O. Chem. Heterocycl.
Compd. 2012, 48, 21-26. (f) Schnurch, M.; Dastbaravardeh, N.;
Ghobrial, M.; Mrozek, B.; Mihovilovic, M. D. Curr. Org. Chem.
2011, 15, 2694-2730. (g) Bellina, F.; Rossi, R. Tetrahedron 2009,
65, 10269-10310.
1
4.2.15 Compound 4o: yellow solid. mp: 189-190 °C. H NMR
(CDCl3, 500 MHz, TMS) δ 7.63 (d, J = 7.5 Hz, 2H), 7.60 (d, J =
7.5 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.39 (t, J = 7.5 Hz, 2H),
7.30-7.27 (m, 3H), 6.73 (dd, J = 17.5, 11.0 Hz, 1H), 5.78 (d, J =
17.5 Hz, 1H), 5.27 (d, J = 11.0 Hz, 1H). 13C NMR (CDCl3, 125
MHz) δ 143.6, 143.3, 136.8, 136.2, 134.3, 133.7, 128.9, 127.5,
126.7, 125.63, 125.61, 124.04, 123.97, 113.9. IR (neat) ν 3055,
2920, 2858, 1624, 1601, 1489, 1455, 1407, 1278, 1202, 1180,
1118, 990, 938, 903, 840, 805 cm-1. MS (ESI): 263 [M+H]+;
HRMS (ESI) calcd for C18H15S [M+H]+: 263.0899; found:
263.0896.
2. For some recent selected examples using aryl bromides and
iodides, please see: (a) Luo, B.-T.; Liu, H.; Lin, Z.-J.; Jiang, J.-X.;
Shen, D.-S.; Liu, R.-Z.; Ke, Z.-F.; Liu, F.-S. Organometallics
2015, 34, 4881-4894. (b) Li, Y.-B.; Wang, J.-R.; Huang, M.-M.;
Wang, Z.-W.; Wu, Y.-S.; Wu, Y.-J. J. Org. Chem. 2014, 79, 2890-
2897. (c) Dao-Huy, T.; Haider, M.; Glatz, F.; Schnürch, M.;
1
4.2.16 Compound 4p: white solid. mp: 158-159 °C. H NMR
(CDCl3, 500 MHz, TMS) δ 7.62 (d, J = 7.5 Hz, 2H), 7.58 (t, J =
6.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.30-7.24 (m, 2H), 7.20 (s,
1H), 7.07 (t, J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ