Highly Efficient Route to Diselenides
FULL PAPERS
were characterized by NMR spectroscopy and comparison Acknowledgements
with authentic samples for known compounds, and also by ele-
mental analysis for the new compounds.
We are grateful to the “Hundred Talented Program” Funding of
the Chinese Academy of Sciences and the National Science
Foundation of China (Grant No. 20406020) for support of this
research.
1
Bis(2-hydroxybenzyl) diselenide (2 g): mp 92–938C; H
NMR (400 MHz, CDCl , 238C): d¼7.17 (t), 7.12 (d), 6.91 (t),
3
6
3
.84 (d) (2:2:2:2 CH, aromatic CH), 5.79 (br, 2H, 2ꢁOH),
13 1
.98 (s, 4H, SeCH ); C{ H} NMR (400 MHz, CDCl , 238C):
2
3
d¼153.72 (s, Cq, CꢀO), 125.42 (s, Cq, i-C of phenyl), 130.92,
1
2
3
29.15, 121.18, 116.63 (s each, 2:2:2:2 CH, aromatic CH),
7.85 (s, SeCH ); anal. calcd. for C H O Se : C 45.18, H
2
14 14
2
2
References
.79; found: C 44.96, H 3.67.
Bis(4-hydroxybenzyl) diselenide (2 h): mp 1488C; H NMR
1
[
1] a) D. Liotta, Acc. Chem. Res. 1984, 17, 28; b) A. Krief, in:
Comprehensive Organometallic Chemistry, (Eds.: E. W.
Abel, F. G. A. Stone, G. Wilkinson, A. Mckillop), Perga-
mon: Oxford, 1995, Vol. II, p. 516; c) Organoselenium
Chemistry – A Practical Approach, (Ed.: T. G. Back),
Oxford University Press: Oxford, 1999; d) G. Mugesh,
W. du Mont, H. Sies, Chem. Rev. 2001, 101, 2125.
(
400 MHz, DMSO-d , 238C): d¼9.41 (s, 2H, 2ꢁOH), 7.05,
6
6
4
1
.69 (d each, J¼7.6 and 7.8 Hz, 4:4H, aromatic CH), 3.84 (s,
13 1
H, SeCH ); C{ H} NMR (400 MHz, DMSO-d , 238C): d¼
2
6
56.53 (s, Cq, CꢀO), 130.14, 115.15 (s each, 4:4 CH, aromatic
CH), 129.05 (s, Cq, i-C of phenyl), 31.71 (s, SeCH ); anal. calcd.
2
for C H O Se : C 45.18, H 3.79; found: C 44.73, H 3.77.
1
4
14
2
2
1
Bis(3-phenylpropyl) diselenide (2k): H NMR (400 MHz,
[
2] Recent leading references, see: a) N. Taniguchi, T. Ona-
mi, J. Org. Chem. 2004, 69, 915; b) T. Nishino, M. Okada,
T. Kuroki, T. Watanabe, Y. Nishiyama, N. Sonoda, J.
Org.Chem. 2002, 67, 8696; c) G. ten Brink, J. Vis,
I. W. C. E. Arends, R. A. Sheldon, J. Org. Chem. 2001,
CDCl , 238C): d¼7.37, 7.28 (m each, 4:6H, aromatic CH),
3
2
2
.98, 2.81 (t each, 4:4 CH, SeCH and PhCH ), 2.15 (m, 4H,
2 2
13
1
ꢁCH ); C{ H} NMR (400 MHz, CDCl , 238C): d¼141.36
2
3
(
s, Cq, i-C of phenyl), 128.59, 128.49, 126.05 (s each, 4:4:2
CH, aromatic CH), 35.49, 32.46 (s each, SeCH and PhCH ),
2
2
2
6
6, 2429; d) M. Iwaoka, H. Komatsu, T. Katsuda, S. To-
9.25 (s, CH ).
2
1
moda, J. Am. Chem. Soc. 2004, 126, 5309 and references
therein; e) B. C. Ranu, T. Mandal, S. Samanta, Org. Lett.
Bis(2-furfuryl) diselenide (2 m): H NMR (400 MHz,
CDCl , 238C): d¼7.39 (d, J¼1.5 Hz, 2H, 5-H), 6.34 (t, J¼
3
2
003, 5, 1439; f) I. Andreadou, W. M. P. B. Menge,
4
.2 Hz, 2H, 4-H), 6.22 (d, J¼3.1 Hz, 2H, 3-H), 3.94 (s, 4H,
13 1
J. N. M. Commandeur, E. A. Worthington, N. P. E. Ver-
meulen, J. Med. Chem. 1996, 39, 2040; g) F. C. Meotti,
E. C. Stangherlin, G. Zeni, C. W. Nogueira, J. B. T. Ro-
cha, Environment. Res. 2004, 94, 276.
SeCH ); C{ H} NMR (400 MHz, CDCl , 238C): d¼151.84
2
3
(
(
3
s, Cq, C-2), 142.25 (s, CH, C-5), 110.91 (s, CH, C-3), 108.45
s, CH, C-4), 24.13 (s, SeCH ); anal. calcd. for C H O Se : C
2
10 10
2
2
7.52, H 3.15; found: C 37.62, H, 3.26.
Bis(3-indolylmethyl) diselenide (2o): H NMR (400 MHz,
1
[3] a) D. L. Klayman, T. S. Griffin, J. Am. Chem. Soc. 1973,
95, 197; b) A. Krief, M. Derock, Tetrahedron Lett. 2002,
43, 3083; c) J. Q. Li, W. L. Bao, P. Lue, X. Zhou, Synth.
Commun. 1991, 21, 799.
[4] a) L. Syper, J. Młochowski, Tetrahedron 1988, 44, 6119;
b) D. P. Thompson, P. Boudjouk, J. Org. Chem. 1988,
53, 2109.
[5] a) A. Krief, T. V. Wemmel, M. Redon, W. Du Mont, C.
Delmotte, Angew. Chem. Int. Ed. 1999, 38, 2245; b) C.
Santi, G. Fragale, T. Wirth, Tetrahedron: Asymmetry
1998, 9, 3625; c) H. J. Reich, C. P. Jasperse, J. M. Renga,
J. Org. Chem. 1986, 51, 2981; d) J. Wang, W. Cui, Y.
Hu, J. Chem. Soc. Perkin Trans. 1 1994, 2341; e) H. Eg-
gert, O. Nielsen, L. Henriksen, J. Am. Chem. Soc. 1986,
108, 1725.
DMSO-d , 238C): d¼7.56 (d), 7.34 (d), 7.20 (s), 7.08 (t), 7.02
6
1
3
1
(
(
(
t) (2:2:2:2:2 CH), 4.14 (s, 4 H, SeCH ); C{ H} NMR
2
400 MHz, DMSO-d , 238C): d¼136.37 (s, Cq, C-9), 126.30
6
s, Cq, C-4), 124.48, 121.36, 118.87, 118.64 (s each, 1:1:1:1
CH, aromatic CH), 111.60 (s, CH. C-2), 111.46 (s, Cq, C-3),
3.38 (s, SeCH ).
2
2
1
Bis(1-phenylethyl) diselenide (4a): mp 54–558C; H NMR
(
400 MHz, CDCl , 238C): d¼7.36–7.25 (m, 10H, aromatic
3
CH), 4.03, 3.88 (q each, 1:1H, SeCH ), 1.74, 1.73 (d each,
2
13
1
3
1
:3H, 2ꢁCH ); C{ H} NMR (400 MHz, CDCl , 238C): d¼
3
3
43.53 (s, Cq, i-C of phenyl), 128.51, 127.54, 127.42 (s each, ar-
omatic CH), 41.39 (s, CH), 21.78 (s, CH ); anal. calcd. for C H
Se : C 52.19, H 4.93 found: C 52.13, H 4.88.
3
16 18
2
1
Bis[1-(3’-methoxyphenyl)ethyl] diselenide (4b): H NMR
(
400 MHz, CDCl , 238C): d¼7.25 (m), 6.94–6.82 (m), 6.83
[6] a) P. Salama, C. Bernard, Tetrahedron Lett. 1995, 36,
5711; b) K. R. Prabhu, S. Chandrasekaran, Chem. Com-
mun. 1997, 1021; c) A. Krief, C. Delmotte, W. Dumont,
Tetrahedron Lett. 1997, 38, 3079; d) A. Krief, C. Del-
motte, W. Dumont, Tetrahedron 1997, 53, 12147; e) P.
Salama, C. Bernard, Tetrahedron Lett. 1998, 39, 745;
f) E. Block, M. Birringer, C. He, Angew. Chem. Int.
Ed. 1999, 38, 1604; g) A. Krief, W. Dumont, C. Delmotte,
Angew. Chem. Int. Ed. 2000, 39, 1669.
3
(
s) (2:4:2 H, aromatic CH), 4.03, 3.98 (q each, 1:1H, SeCH),
3
.84 (d, 6H, 2ꢁOCH ), 1.76, 1.73 (d each, 6H, 2ꢁCH );
3
3
13
1
C{ H} NMR (400 MHz, CDCl , 238C): d¼159.59 (s, Cq,
3
CꢀO), 145.07 (s, Cq, i-C of phenyl), 129.44 (s), 119.77 (s),
1
13.16 (d), 112.69 (d) (aromatic CH), 55.27 (s, OCH ), 41.35
3
(
s, SeCH), 21.89, 21.72 (s each, CH ): anal. calcd. for C H
3 18 22
O Se : C 50.48, H 5.18; found: C 50.70, H 5.14.
2
2
1
Bis(3-heptyl) diselenide (4f): H NMR (400 MHz, CDCl ,
3
2
0
2
38C): d¼2.87 (m, 2H, SeCH), 1.67, 1.33 (m each, 8 X CH ),
[7] V. Saravanan, E. Porhiel, S. Chandrasekaran, Tetrahe-
dron Lett. 2003, 44, 2257.
[8] X. Zhang, M. Ruan, W. Fan, Synth. Commun. 1996, 26,
4665.
2
1
3
1
.98, 0.91 (t each, 4ꢁCH ); C{ H} NMR (400 MHz, CDCl ,
3
3
38C): d¼48.81 (s, SeCH), 35.22, 30.11, 28.74, 22.70 (s each,
CH ), 14.19, 12.28 (s each, CH ).
2
3
Adv. Synth. Catal. 2005, 347, 877–882
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