454
T. Ozaki et al. / Journal of Organometallic Chemistry 696 (2011) 450e455
(400 MHz) using CDCl3 as the solvent with tetramethylsilane (TMS)
as the internal standard. 13C NMR spectra were obtained on a JEOL
JNM-ECX400 spectrometer (100 MHz) using CDCl3 as the solvent.
Chemical shifts in 13C NMR were measured relative to CDCl3 by
(C), 129.4 (CH), 130.4 (CH), 132.1 (CH), 133.6 (C), 135.0 (CH). HRMS
(FAB) Calcd for [M þ Hþ] C12H14NSe: 252.0291, Found 252.0285.
4.2.4. 1-Phenyl-2-phenylseleno-1-propene (4e)
using
d
77.0 ppm. High resolution mass spectra were obtained on
A mixture of E and Z isomers; white oil; (E)-4e: 1H NMR (CDCl3):
a JEOL JMS-700 instrument supported by Kyoto-Advanced Nano-
technology Network.
d d 45.0
3.6 (s, 3H), 7.08 (s,1H), 7.23e7.51 (m,10H). 13C NMR (CDCl3):
(CH3), 126.7 (CH), 127.5 (C), 127.6 (CH), 128.4 (CH), 129.1 (CH), 129.3
(CH), 129.4 (C), 129.8 (C), 132.5 (CH), 133.4 (CH). (Z)-4e: 1H NMR
(CDCl3):
(CDCl3):
d
3.6 (s, 3H), 7.10 (s, 1H), 7.23e7.51 (m, 10H), 13C NMR
29.7 (CH3), 126.7 (CH), 127.5 (C), 127.6 (CH), 128.4 (CH),
4.2. Preparation of 2-phenylseleno-2-octene (4a)
d
128.6 (CH), 129.3 (CH), 129.4 (C), 129.8 (C), 131.0 (CH), 133.4 (CH).
HRMS (FAB) Calcd for [M þ Hþ] C15H15Se: 275.0339, Found
275.0330.
Into a two-necked flask equipped with a reflux condenser and
a magnetic stirring bar were placed PdCl2(PPh3)2 (14.0 mg,
0.02 mmol), benzene (0.5 mL), alkyne (1.0 mmol), and benzene-
selenol (106
m
L, 1.0 mmol) under N2 atmosphere. The mixture was
4.2.5. 5-Phenylseleno-4-hexen-1-ol (4f)
heated at 80 ꢀC with stirring for 16 h. After the reaction was
complete, the resulting mixture was evaporated, and the products
were purified by preparative TLC on silica gel with a mixed solvent
of hexane/ethyl acetate as an eluent. The purification of the product
4a was performed by preparative TLC (PTLC) on silica gel and/or
a recycling preparative HPLC (Japan Analytical Industry Co. Ltd.,
Model LC-908) equipped with JAIGEL-1H and -2H columns (GPC,
using CHCl3 as an eluent). 4a: a mixture of E and Z isomers; white
Colorless oil; (E)-4f: 1H NMR (CDCl3):
d
2.00 (s, 3H), 2.28e2.37
(m, 2H), 3.54 (t, J ¼ 6.0 Hz, 2H), 5.77 (dt, J ¼ 1.4, 6.8 Hz, 1H),
7.22e7.31 (m, 5H). 13C NMR (CDCl3):
25.8 (CH3), 29.7 (CH2), 32.1
(CH2), 62.3 (CH2), 127.0 (C), 128.4 (CH), 129.2 (CH), 129.3 (CH), 131.7
(C), 133.0 (CH). (Z)-4f: 1H NMR (CDCl3):
2.00 (s, 3H), 2.16e2.23 (m,
2H), 3.54 (t, J ¼ 6.0 Hz, 2H), 5.92 (dt, J ¼ 1.4, 7.3 Hz, 1H), 7.22e7.31
(m, 5H). 13C NMR (CDCl3):
25.7 (CH3), 29.7 (CH2), 31.9 (CH2), 62.2
d
d
d
(CH2), 127.0 (C), 128.4 (CH), 129.2 (CH), 129.3 (CH), 131.7 (C), 133.0
(CH). HRMS (FAB) Calcd for [M þ Hþ] C11H15OSe: 243.0288, Found
243.0293.
oil; (E)-4a: 1H NMR (CDCl3):
6H), 2.00 (s, 3H), 2.24e2.29 (m, 2H), 5.79 (dt, J ¼ 1.4, 7.1 Hz, 1H),
7.25e7.27 (m, 3H), 7.44e7.45 (m, 2H). 13C NMR (CDCl3):
14.1 (CH3),
d
0.90 (t, J ¼ 6.9 Hz, 3H), 1.29e1.45 (m,
d
20.0 (CH2), 22.5 (CH2), 28.9 (CH2), 29.5 (CH2), 31.4 (CH3), 125.3 (C),
4.2.6. 1,2-Bis(phenylseleno)-3-{(tetrahydro-2H-pyran-2-yl)oxy}-1-
126.8 (CH), 129.0 (CH), 132.5 (CH), 133.0 (C), 137.9 (CH). (Z)-4a: 1H
propene (6g)
NMR (CDCl3):
3H), 2.08e2.14 (m, 2H), 5.97 (dt, J ¼ 1.4, 7.3 Hz, 1H), 7.25e7.27 (m,
3H), 7.44e7.45 (m, 2H). 13C NMR (CDCl3):
14.1 (CH3), 20.0 (CH2),
d
0.90 (t, J ¼ 6.9 Hz, 3H), 1.29e1.45 (m, 6H), 2.00 (s,
White oil; 1H NMR (CDCl3):
d 1.46e1.76 (m, 6H), 3.39e3.42 (m,
1H), 3.73e3.79 (m, 1H), 4.17 (dd, J ¼ 13.5, 78.0 Hz, 2H), 4.54 (t,
d
J ¼ 3.2 Hz, 1H), 7.14e7.28 (m, 5H), 7.40 (1H), 7.43e7.54 (m, 2H). 13C
22.5 (CH2), 26.4 (CH2), 28.9 (CH2), 29.2 (CH3), 126.3 (C), 127.8 (CH),
130.0 (CH), 133.5 (CH), 134.0 (C), 138.9 (CH). HRMS (FAB) Calcd for
[M þ Hþ] C14H21Se: 269.0808, Found 269.0809.
NMR (CDCl3): d 19.1 (CH2), 25.2 (CH2), 30.2 (CH2), 61.8 (CH2), 71.2
(CH), 97.4 (CH2), 127.1 (CH), 127.5 (C), 129.1 (CH), 132.2 (CH), 132.7
(CH), 133.9 (CH). HRMS (FAB) Calcd for [M þ Hþ] C20H22O2Se2:
453.9950, Found 453.9954.
4.2.1. 5-Methyl-2-phenylseleno-2-hexene (4b)
A mixture of E and Z isomers; white oil; (E)-4b: 1H NMR (CDCl3):
Acknowledgements
d
0.91 (d, J ¼ 6.8 Hz, 6H), 1.57 (s, 3H), 1.64e1.72 (m, 1H), 2.25e2.29
(m, 2H), 5.80 (t, J ¼ 7.1 Hz,1H), 7.17e7.28 (m, 3H), 7.43e7.54 (m, 2H).
13C NMR (CDCl3):
20.1 (CH), 22.3 (CH3), 28.6 (CH2), 38.6 (CH3),
126.8 (CH), 128.9 (C), 129.0 (CH), 132.6 (CH), 134.9 (C), 136.6 (CH).
(Z)-4b: 1H NMR (CDCl3):
0.91 (d, J ¼ 6.8 Hz, 6H), 1.57 (s, 3H),
1.64e1.72 (m, 1H), 2.13e2.19 (m, 2H), 5.97 (t, J ¼ 7.5 Hz, 1H),
7.17e7.28 (m, 3H), 7.43e7.54 (m, 2H). 13C NMR (CDCl3):
20.1 (CH),
22.3 (CH3), 27.9 (CH2), 37.9 (CH3), 126.8 (CH), 128.9 (C), 129.0 (CH),
131.4 (CH), 134.9 (C), 136.4 (CH). HRMS (FAB) Calcd for [M þ Hþ]
C13H19Se: 255.0652, Found 255.0646.
This work was supported by a Grant-in-Aid for Scientific
Research (B, 19350095) from the Ministry of Education, Culture,
Sports, Science and Technology, Japan, and also supported by
Kyoto-Advanced Nanotechnology Network.
d
d
d
References
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2002, pp. 2841e2849.
4.2.2. (E)-5-chloro-2-phenylseleno-2-pentene (4c)
Colorless oil; (E)-4c: 1H NMR (CDCl3):
d
2.01 (s, 3H), 2.55e2.60
(m, 2H), 3.53 (t, J ¼ 6.9 Hz, 2H), 5.85 (dt, J ¼ 1.4, 7.1 Hz, 1H),
7.25e7.28 (m, 4H), 7.45e7.46 (m, 1H). 13C NMR (CDCl3):
21.0 (CH3),
d
[2] (a) A. Ogawa, J. Organomet. Chem. 611 (2000) 463e474;
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87e90;
33.6 (CH2), 44.5 (CH2), 128.3 (C), 130.0 (CH), 130.1 (CH), 131.6 (CH),
133.6 (C), 134.4 (CH). HRMS (FAB) Calcd for [M þ Hþ] C11H14ClSe:
260.9949, Found 260.9952.
4.2.3. 5-Phenylseleno-4-hexenenitrile (4d)
A mixture of E and Z isomers; white oil; (E)-4d: 1H NMR (CDCl3):
(b) S.-I. Murahashi, T. Yano, J. Am. Chem. Soc. 102 (1980) 2456e2458;
(c) H.J. Cristau, B. Chabaud, R. Labaudiniere, H. Christol, Organometallics 4
(1985) 657e661;
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(1986) 875e878;
(e) K. Ohe, H. Takahashi, S. Uemura, N. Sugita, J. Org. Chem. 52 (1987)
4859e4863;
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35e47;
d
1.82 (t, J ¼ 7.6 Hz, 2H), 2.03 (s, 3H), 2.60e2.65 (m, 2H), 5.79 (t,
J ¼ 6.6 Hz, 1H), 7.25e7.35 (m, 4H), 7.47e7.53 (m, 1H). 13C NMR
(CDCl3):
d 19.9 (CH3), 29.8 (CH2), 36.7 (CH2), 119.4 (CN), 127.6 (C),
129.4 (CH), 130.4 (CH), 132.1 (CH), 133.6 (C), 135.2 (CH). (Z)-4d: 1H
NMR (CDCl3):
d
1.82 (t, J ¼ 7.6 Hz, 2H), 2.03 (s, 3H), 2.47e2.53 (m,
2H), 5.93 (t, J ¼ 7.3 Hz,1H), 7.25e7.35 (m, 4H), 7.47e7.53 (m,1H). 13C
NMR (CDCl3):
d 19.9 (CH3), 29.5 (CH2), 36.4 (CH2), 119.4 (CN), 127.5