S. Ito et al. / Journal of Organometallic Chemistry 695 (2010) 291–296
295
CDCl3) d = 1.35 (s, 9H, p-tBu), 1.61 (s, 18H, o-tBu), 2.23 (d,
materials were removed in vacuo and the residue was treated with
column chromatography (SiO2, hexane/EtOAc 5:1) to afford
16.5 mg of 18 (92% yield). 18: Colorless oil; 1H NMR (400 MHz,
CDCl3) d = 2.93–2.91 (m, 1H, CH2), 2.97–2.96 (m, 1H, CH2), 3.46–
3.45 (m, 1H, CH2), 3.50–3.49 (m, 1H, CH2), 4.51–4.50 (m, 1H,
C@CH2), 4.94–4.92 (m, 1H, C@CH2) [11].
3
3JPH = 37.6 Hz, 3H, Me), 2.86 (d, JPH = 24.8 Hz, 2H, CH2), 6.74–
4
6.77 (m, 2H, Ph), 7.18–7.20 (m, 3H, Ph), 7.56 (d, JPH = 4.0 Hz, 2H,
Mes*); 31P{1H} NMR (162 MHz, CDCl3) d = 180.4; 13C{1H} NMR
2
(101 MHz, CDCl3) d = 24.9 (d, JPC = 21.5 Hz, Me), 31.0 (s, p-CMe3),
4
34.1 (d, JPC = 1.4 Hz, o-CMe3), 35.2 (s, p-CMe3), 38.9 (s, o-CMe3),
2
3
43.1 (d, JPC = 7.1 Hz, CH2), 123.1 (d, JPC = 16.2 Hz, m-Mes*),
1
123.8 (d, JPC = 6.4 Hz, ipso-Mes*), 126.9 (s, p-Ph), 128.4 (s, m-Ph),
4.10. DFT calculations
3
129.2 (s, o-Ph), 136.1 (d, JPC = 14.7 Hz, ipso-Ph), 154.1 (d,
4JPC = 2.7 Hz, p-Mes*), 156.6 (s, o-Mes*), 175.6 (d, JPC = 73.2 Hz,
1
All computational optimizations for E–G were performed with
the GAUSSIAN 03 package [21] using 6-31G* (for C, H, P) and LanL2DZ
(for Au) basis sets and a B3LYP functional. Initial structures for the
DFT procedures were obtained from ab initio calculations at the
HF/6-31G*/LanL2DZ level.
P@C); ESI-MS calcd for C27H39AuClP+Na, 649.2036, found: m/z
649.2034; Anal. Calc. for C21H39AuClPꢁ0.3H2O: C, 51.28; H, 6.31.
Found: C, 51.20; H, 6.25%.
4.6. Compound E-10
Acknowledgements
A mixture of E-7 (77 mg, 0.20 mmol) and Au(tht)Cl (0.19 mmol)
in dichloromethane (5 mL) was stirred for 12 h at room tempera-
ture. The volatile materials were removed in vacuo and the residue
was washed with hexane to afford 86 mg of E-10 (72% yield): Col-
orless powder, m.p. 156–159 °C (decomp); 1H NMR (400 MHz,
This work was supported in part by the Grant-in-Aid for Scien-
tific Research (No. 20750098) from the Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan, and Casio Science
Promotion Foundation. The authors thank Prof. Fumiyuki Ozawa,
Kyoto University, for his helpful suggestions and comments.
3
CDCl3) d = 1.25 (d, JPH = 28.8 Hz, 3H, Me), 1.31 (s, 9H, p-tBu), 1.54
3
(s, 18H, o-tBu), 3.98 (d, JPH = 31.6 Hz, 2H, CH2), 7.22–7.32 (m, 5H,
4
Ph), 7.50 (d, JPH = 3.6 Hz, 2H, Mes*); 31P{1H} NMR (162 MHz,
CDCl3) d = 180.2; 13C{1H} NMR (101 MHz, CDCl3) d = 22.1 (d,
Appendix A. Supplementary material
4
2JPC = 6.8 Hz, Me), 31.0 (s, p-CMe3), 33.6 (d, JPC = 1.3 Hz, o-CMe3),
2
Supplementary data associated with this article can be found, in
35.2 (s, p-CMe3), 38.7 (s, o-CMe3), 46.2 (d, JPC = 19.6 Hz, CH2),
3
1
123.4 (d, JPC = 9.4 Hz, m-Mes*), 123.8 (d, JPC = 31.6 Hz, ipso-
Mes*), 127.5 (s, p-Ph), 128.5 (s, m-Ph), 128.9 (s, o-Ph), 136.2 (d,
3JPC = 18.5 Hz, ipso-Ph), 154.0 (d, JPC = 2.6 Hz, p-Mes*), 156.2 (d,
4
References
2JPC = 2.0 Hz, o-Mes*), 175.5 (d, JPC = 72.3 Hz, P@C); ESI-MS calcd
1
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3
3
5.09 (d, JHH = 17.6 Hz, 1H, CH), 5.10 (d, JHH = 10.4 Hz, 1H, CH),
3
3
5.58 (brs, 1H, CH), 6.47 (dd, JHH = 17.6 Hz, JHH = 10.4 Hz, 1H, CH)
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3
3
3
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4
4
4
4
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4.9. Cyclization of 17
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