M.-H. Hsu et al. / Tetrahedron 64 (2008) 4268e4274
4273
4.1.2.6. Entry 6: 4-biphenylaldehyde.15,17 White solid, mp
59e60 ꢀC; 1H NMR (300 MHz, CDCl3): d 10.05 (s, 1H),
7.95 (d, J¼8.1 Hz, 2H), 7.75 (d, J¼8.1 Hz, 2H), 7.65e7.62
(m, 2H), 7.50e9.39 (m, 3H); 13C NMR (75 MHz, CDCl3):
d 147.6, 147.0, 138.7, 129.1, 128.9, 127.8, 127.4, 124.1.
reaction mixture was filtered, the yellow precipitate was then
dissolved and filtered through a filter paper by DCM. The sol-
vent was removed under reduced pressure. The resulting solid
was collected and recrystallized from dichloromethane/diethyl
ether to give complex 1 as a yellow-orange solid (1.17 g, yield:
70%). Mp 196e198 ꢀC; 1H NMR (300 MHz, CDCl3): d 6.94e
6.92 (m, 2H), 2.82e2.79 (m, 4H), 2.48e2.36 (m, 4H), 1.91e
1.66 (m, 30H), 1.29e1.17 (m, 12H); 13C NMR (75 MHz,
CDCl3): d 68.3, 66.1, 52.0. Anal. Calcd for C12H26N2O4Pd:
C, 32.78; H, 5.96; N, 6.37. Found: C, 32.40; H, 6.33; N, 6.34.
4.1.2.7. Entry 7: 3-biphenylaldehyde.16 1H NMR (300 MHz,
CDCl3): d 10.08 (s, 1H), 8.10 (s, 1H), 8.49 (dd, J¼7.5,
1.8 Hz, 2H), 7.64e7.58 (m, 3H), 7.50e7.37 (m, 3H); 13C
NMR (75 MHz, CDCl3): d 192.3, 142.1, 139.6, 133.0, 129.4,
128.9, 128.7, 128.1, 127.9, 127.1.
4.1.4. Crystal structure data experimental
4.1.2.8. Entry 8: 4-methylbiphenyl.15,18 White solid, mp 44e
46 ꢀC; 1H NMR (300 MHz, CDCl3): d 7.50 (d, J¼7.5 Hz,
2H), 7.43 (d, J¼8.1 Hz, 2H), 7.35 (dd, J¼7.5, 7.8 Hz, 2H),
7.25 (dd, J¼7.5, 7.5 Hz, 1H) 7.18 (d, J¼8.1 Hz, 2H), 2.40
(s, 3H); 13C NMR (75 MHz, CDCl3): d 141.1, 138.3, 137.0,
129.4, 128.7, 127.0, 126.9, 21.1.
Structure of complex 1, (cryptand-22)PdCl2, has been unam-
biguously identified by X-ray crystallography. Crystals suitable
for X-ray structure analysis were grown from DCM/ether. Ayel-
low crystal with dimensions of 0.5ꢂ0.5ꢂ0.04 mm was mounted
on a glass fiber on a Siemens P4 diffractometer equipped with
monochromated Mo Ka radiation. Intensity data were collected
and reduced by using well-established software package
XSCANS.22 The structure was solved by direct method and
was refined using SHELXTL.23 All non-hydrogen atoms were
located from difference maps and refined anisotropically.
H-atoms attached on the two N-atoms were found from differ-
ence maps and isotropically refined as normal atoms. The rest
of the H-atoms were placed at idealized positions. The final re-
siduals of the refinement were R1¼0.0431, wR2¼0.0969, and
S¼1.041. Crystal data in CIF format can be found in the supple-
mentary data.
4.1.2.9. Entry 9: 4-methoxybiphenyl.17,19 White solid, mp 82e
84 ꢀC; 1H NMR (300 MHz, CDCl3): d 7.54 (dd, J¼7.2,
6.9 Hz, 4H), 7.38 (dd, J¼7.5, 7.5 Hz, 2H), 7.30 (dd, J¼7.2,
7.2 Hz, 1H), 6.97 (d, J¼6.9 Hz, 2H), 3.85 (s, 3H); 13C NMR
(75 MHz, CDCl3): d 159.1, 140.8, 133.7, 128.7, 128.1,
126.7, 126.6, 114.1, 55.3.
4.1.2.10. Entry 10: 4-cyano-40-methoxybiphenyl.18,20 White
1
solid, mp 178e180 ꢀC; H NMR (300 MHz, CDCl3): d 7.7e
7.62 (m, 2H), 7.55e7.52 (m, 2H), 7.02 (t, 2H), 6.9 (t, 2H),
3.86 (s, 3H); 13C NMR (75 MHz, CDCl3): d 160.2, 145.2,
132.5, 131.5, 128.3, 127.1, 119.1, 114.5, 110.1, 55.42.
5. Supplementary data
Crystallographic data for the structure of complex 1 has
been deposited with the Cambridge Crystallographic Data
Centre as supplementary publication number CCDC 665828.
Copies of the data can be obtained, free of charge, on applica-
tion to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
4.1.2.11. Entry 11: 4-trifluoromethyl-40-methoxybiphenyl.17,18
1
White solid, mp 122e124 ꢀC; H NMR (300 MHz, CDCl3):
d 7.67e7.64 (m, 4H), 7.55e7.50 (d, J¼8.7 Hz, 2H), 7.0e
6.97 (d, J¼8.6 Hz, 2H), 3.85 (s, 3H); 13C NMR (75 MHz,
CDCl3): d 159.8, 144.3, 132.2, 128.4, 126.8, 126.2, 125.6,
122.6, 114.4, 55.37.
Acknowledgements
4.1.2.12. Entry 12: 4-tert-butyl-40-methoxybiphenyl.21 White
1
solid, mp 127e128 ꢀC; H NMR (300 MHz, CDCl3): d 7.54
We thank Soochow University for support of this work.
References and notes
(d, J¼8.9 Hz, 2H), 7.49 (d, J¼8.7 Hz, 2H), 7.43 (d,
J¼8.7 Hz, 2H), 6.98 (d, J¼8.9 Hz, 2H), 3.85 (s, 3H), 1.37
(s, 9H); 13C NMR (75 MHz, CDCl3): d 158.9, 149.6, 137.9,
133.6, 128.0, 126.3, 125.6, 114.1, 55.3, 34.5, 31.4.
1. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (b) Suzuki, A.
Metal-catalyzed Cross-coupling Reactions; Diederich, F., Stang, P. J.,
Eds.; Wiley-VCH: Weinheim, 1998; pp 49e97 and references therein;
(c) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998, 120, 7369;
(d) Reetz, M. T.; Lohmer, G.; Schwickardi, R. Angew. Chem., Int. Ed.
1998, 37, 481; (e) Littke, A. F.; Fu, G. C. J. Org. Chem. 1999, 64, 10;
(f) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 36, 3437.
2. (a) Stanforth, S. P. Tetrahedron 1998, 54, 263; (b) Suzuki, A. J. Organo-
met. Chem. 1999, 576, 147; (c) Kotha, S.; Lahiri, K.; Kashinath, D. Tetra-
hedron 2002, 58, 9633.
4.1.2.13. Entry 13: 4,40-dimethoxybiphenyl.15,18 White solid,
1
mp 180e182 ꢀC; H NMR (300 MHz, CDCl3): d 7.49e7.46
(d, J¼9.3 Hz, 4H), 6.97e6.94 (d, J¼8.7 Hz, 4H), 3.84 (s,
6H); 13C NMR (75 MHz, CDCl3): d 158.7, 133.5, 127.7,
114.1, 55.4.
4.1.3. Synthesis of (cryptand-22)PdCl2
3. (a) Smith, G. B.; Dezeny, G. C.; Hughes, D. L.; King, A. O.; Verhoeven,
T. R. J. Org. Chem. 1994, 59, 8151; (b) Nicolaou, K. C.; Boddy, C. N. C.;
Brase, S.; Winssinger, N. Angew. Chem., Int. Ed. 1999, 38, 2096.
4. (a) Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513; (b)
Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1998, 37, 3387; (c) Littke,
Cryptand-22 (118.1 mg, 0.45 mmol) was added into a solu-
tion of Na2PdCl4 (117.7 mg, 0.4 mmol) in ethanol (30 mL) at
room temperature. The mixture was stirred at room temperature
for 2.5 h, during which a yellow precipitate appeared. After the