Cui et al.
FULL PAPER
solvents were removed under vacuum to give a yellow
solid. After that, allyl carbonate 2 (0.24 mmol, 120
mol%), sodium phenyl selenide 1 (0.20 mmol), and
DCE (2.0 mL) were added. The reaction mixture was
stirred at room temperature until the mixture became
clear. Then the crude reaction mixture was filtered
through celite and the solvent was removed under re-
duced pressure. The ratio of regioisomers (branched to
126.2, 119.0, 113.1, 111.6, 91.7, 55.2, 30.6; IR (KBr) ν:
3054, 2934, 2841, 1645, 1566, 1430, 1263, 1147, 971,
-
+
1
702, 659 cm . HRMS (EI) calcd for C16H16OSe (M ):
304.0366, found 304.0367.
(E)-Phenyl(3-(3-(trifluoromethyl)phenyl)allyl)sel-
ane (3f) White solid, m.p. 54.8—55.8 ℃, yield: 49.9
1
mg (73%). H NMR spectroscopy showed a 99∶1 lin-
1
ear∶branched ratio. H NMR (400 MHz, CDCl3) δ:
1
linear) was determined by H NMR of the crude reac-
7.53—7.51 (m, 2H), 7.48 (s, 1H) 7.46—7.38 (m, 3H),
7.27—7.26 (m, 3H), 6.39 (dt, J=15.6, 7.6 Hz, 1H),
6.20 (d, J=15.6 Hz, 1H), 3.68 (d, J=7.6 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ: 137.6, 134.2, 130.9 (q, J=
31.9 Hz), 130.5, 129.5, 129.3, 129.0, 128.9, 128.0,
127.6, 124.1 (q, J=270.7 Hz), 123.9 (q, J=3.8 Hz),
122.9 (q, J=3.8 Hz), 30.4; 19F NMR (376 MHz, CDCl3)
δ: -62.63 (s); IR (KBr) ν: 3050, 2941, 1579, 1476,
1449, 1333, 1300, 1180, 1127, 1064, 991, 951, 891, 791,
tion mixture or the mixture of these two compounds.
The crude residue was purified by flash column chro-
matography (petroleum ether/dichloromethane) to give
the desired products.
The phosphoramidite ligands,[13] substituted allyl
carbonates,[14] and sodium phenyl selenide[15] were pre-
pared according to known procedures.
(E)-Cinnamyl(phenyl)selane (3a)[16] White solid,
-
+
1
1
m.p. 64.3—65.1 ℃, yield: 40.5 mg (72%). H NMR
745, 729, 705, 685, 662 cm . MS (EI) m/z: 342 (M ).
HRMS (EI) calcd for C16H13F3Se (M+ ): 342.0135,
found 342.0138.
spectroscopy showed a 99∶1 linear∶branched ratio.
1H NMR (400 MHz, CDCl3) δ: 7.53—7.51 (m, 2H),
7.28—7.18 (m, 8 H), 6.33 (dt, J=15.6, 7.6 Hz, 1H),
6.23 (d, J=15.6 Hz, 1H), 3.69 (d, J=7.6 Hz, 2H).
(E)-(3-(4-Methoxyphenyl)allyl)(phenyl)selane (3b)[17]
White solid, m.p. 89.7—91.0 ℃, yield: 34.1 mg
(56%). 1H NMR spectroscopy showed a 99 ∶ 1
linear∶branched ratio. 1H NMR (400 MHz, CDCl3) δ:
7.53—7.51 (m, 2H), 7.26—7.20 (m, 5H), 6.82 (d, J=
8.8 Hz, 2H), 6.23—6.13 (m, 2H), 3.79 (s, 3H), 3.67 (d,
J=6.4 Hz, 2H).
(E)-2-(3-(Phenylselanyl)prop-1-enyl)thiophene
(3g) White solid, m.p. 56.7—57.4 ℃, yield: 21.3 mg
1
(38%). H NMR spectroscopy showed a 99∶1 linear∶
1
branched ratio. H NMR (300 MHz, CDCl3) δ: 7.53—
7.51 (m, 2H), 7.27—7.25 (m, 3H), 7.11 (d, J=5.2 Hz,
1H), 6.92 (dd, J=7.6, 7.6 Hz, 1H), 6.84 (d, J=3.2 Hz,
1H), 6.36 (d, J=15.6 Hz, 1H), 6.16 (dt, J=15.6, 7.6 Hz,
1H), 3.56 (d, J=7.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ: 141.8, 134.0, 129.7, 129.0, 127.4, 127.3,
(E)-(3-(4-Chlorophenyl)allyl)(phenyl)selane (3c)[17]
Lemon yellow solid, m.p. 72.7—73.5 ℃, yield: 31.4
125.6, 125.3, 125.2, 124.0, 30.5; IR (KBr) ν: 3468, 2353,
1696, 1679,1636, 1632, 1257, 950, 725, 696 cm-
.
1
mg (51%). H NMR spectroscopy showed a 99∶1 lin-
HRMS (EI) calcd for C13H12SSe (M+): 279.9825, found
279.9853.
1
1
ear∶branched ratio. H NMR (400 MHz, CDCl3) δ:
7.52—7.50 (m, 2H), 7.26—7.23 (m, 5H), 7.18 (d, J=
8.8 Hz, 2H), 6.28 (dt, J=15.6, 7.6 Hz, 1H), 6.15 (d,
J=15.6 Hz, 1H), 3.66 (d, J=7.6 Hz, 2H).
(E)-Phenyl(5-phenylpent-2-enyl)selane
(3h)[18]
1
Yellow oil, yield: 40.4 mg (67%). H NMR spectro-
scopy showed a 99∶1 linear∶branched ratio. 1H NMR
(400 MHz, CDCl3) δ: 7.49—7.46 (m, 2H), 7.28—7.24
(m, 5H), 7.17 (t, J=7.2 Hz, 1H), 7.10 (d, J=7.2 Hz,
2H), 5.60 (dt, J=15.2, 7.2 Hz, 1H), 5.42 (dt, J=15.2,
6.4 Hz, 1H), 3.48 (d, J=7.6 Hz, 2H), 2.56 (t, J=7.6 Hz,
2H), 2.27 (dt, J=8.0, 7.2 Hz, 2H).
(E)-Phenyl(3-p-tolylallyl)selane (3d)[6]
White
1
solid, m.p. 67.0—68.2 ℃, yield: 39.2 mg (68%). H
NMR spectroscopy showed a 99∶1 linear∶branched
1
ratio. H NMR (400 MHz, CDCl3) δ: 7.52—7.50 (m,
2H), 7.24—7.22 (m, 3H), 7.16 (d, J=8 Hz, 2H), 7.07 (d,
J=8 Hz, 2H), 6.27 (dt, J=15.6, 7.2 Hz, 1H), 6.20 (d,
J=15.6 Hz, 1H), 3.66 (d, J=6.8 Hz, 2H), 2.31 (s, 3H);
13C NMR (100 MHz, CDCl3) δ: 137.2, 134.0, 133.9,
132.0, 130.0, 129.1, 128.9, 127.2, 126.1, 124.8, 30.8,
21.1; IR (KBr) ν: 3428, 2917, 2362, 1645, 1629, 1565,
(E)-Hex-2-enyl(phenyl)selane (3i)[19] Yellow oil,
1
yield: 25.9 mg (54%). H NMR spectroscopy showed a
1
89∶11 linear∶branched ratio. H NMR (400 MHz,
CDCl3) δ: 7.53—7.47 (m, 2H), 7.25—7.24 (m, 3H),
6.56 (dt, J=15.2, 7.6 Hz, 1H), 5.39 (dt, J=15.2, 6.8 Hz,
1H), 3.50 (d, J=7.2 Hz, 2H), 1.93 (dt, J=7.2, 7.2 Hz,
2H), 1.33—1.24 (m, 2H), 0.82 (t, J=7.2 Hz, 3H).
-
1
1503, 1469, 1263, 1021, 757, 699, 662 cm . MS (EI)
m/z: 288 (M+). HRMS (EI) calcd for C16H16Se (M+):
288.0417, found 288.0414.
Synthesis of compounds 5
(E)-(3-(3-Methoxyphenyl)allyl)(phenyl)selane (3e)
1
[Ir(COD)Cl]2 (0.0060 mmol, 3.0 mol%), [O,O'-(S)-
(1,1'-dinaphthyl-2,2'-diyl)-N,N'-di-(S,S)-[phenylethyl-
phosphoramidite] (L1, 0.0012 mmol, 6.0 mol%), THF
(0.5 mL), and propylamine (0.2 mL) were placed in a
dry Schlenk tube filled with argon. The reaction mixture
was heated at 50 ℃ for 30 min and then the volatile
solvents were removed under vacuum to give a yellow
solid. After that, allyl carbonate 2 (0.24 mmol, 120
Yellow oil, yield: 39.5 mg (65%). H NMR spectro-
scopy showed a 99∶1 linear∶branched ratio. 1H NMR
(400 MHz, CDCl3) δ: 7.53—7.51 (m, 2H), 7.26—7.25
(m, 3H), 7.19 (t, J=8.0 Hz, 1H), 6.87 (d, J=7.6 Hz,
1H), 6.81 (s, 1H), 6.76 (d, J=8 Hz, 1H), 6.32 (dt, J=
15.6, 7.6 Hz, 1H), 6.20 (d, J=15.6 Hz, 1H), 3.80 (s,
3H), 3.68 (d, J=7.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ: 159.7, 138.3, 134.0, 132, 129.4, 129.0, 127.4,
2648
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2647—2651