TABLE 1. Red u ctive Selen a tion of Ben za ld eh yd e (1a ) to
Diben zyl Diselen id e (1b)
Efficien t Red u ctive Selen a tion of Ar om a tic
Ald eh yd es to Sym m etr ica l Diselen id es w ith
Se/CO/H O u n d er Atm osp h er ic P r essu r e
2
entrya
solvent
THF
temp (°C)
H
O (mL)
yield (%)b
2
1
2
3
4
5
6
7
8
9
60
95
75
75
95
95
95
23
60
80
95
95
95
95
2
2
2
2
2
2
2
2
2
2
2
0
1
4
1,4-dioxane
CH CN
Fengshou Tian, Zhengkun Yu,* and Shiwei Lu*
3
EtOH
DMACc
DMSO
FP
National Engineering Research Center for Catalysis,
Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, 457 Zhongshan Road,
Dalian, Liaoning 116023, P. R. China
15
65
d
DMF
DMF
DMF
DMF
DMF
DMF
DMF
67
85
94
1
11
1
1
14
0
2
3
60
94
Received February 14, 2004
a
Reaction conditions: benzaldehyde, 2.5 mmol; Se, 2.5 mmol;
b
Abstr a ct: An efficient method for the synthesis of sym-
metrical diselenides is described. Reductive selenation of
aromatic and heterocyclic aromatic aldehydes (ArCHO) with
Se/CO/H2O in DMF afforded diselenides (ArCH2SeSeCH2-
Ar) in yields up to 94% under atmospheric pressure without
use of a base.
bubbling CO, 0.1 MPa; solvent, 20 mL; 7.0 h. Isolated yield of
c
1
b. DMAC ) N,N-dimethylacetamide. d FP ) 1-formylpiperidine.
thesized from the reactions of aldehydes with sodium
hydrogen selenide in the presence of an amine and
sodium borohydride.10 Huang et al. reported that alde-
hydes reacted with elemental selenium and sodium
borohydride to afford dibenzyl diselenides in the absence
of an amine.11 However, most of the known methods for
preparation of diselenides suffer from disadvantages such
as use of strong reducing agents and highly toxic gas,
harsh reaction conditions, low yields, or complicated
manipulations. Sonoda et al. discovered that elemental
selenium can be readily reduced by carbon monoxide and
water in the presence of base to produce hydrogen
selenide, which was successfully applied to the synthesis
of aliphatic diselenides from both aliphatic ketones and
Organic diselenides, as useful synthetic reagents and
intermediates, play an important role in organoselenium
chemistry because they are stable, easily handled, and
reactive enough to produce electrophilic, nucleophilic, and
radicophilic species.1 General routes to organic dis-
elenides involve reactions of metal diselenides with alkyl
2
3-5
halides, dimerization with seleno-cyanates,
and oxi-
6
7
dation of selenols or selenolates. Carbonyl compounds
have also been used for this purpose. Both Margolis and
Cohen reported that treatment of carbonyl compounds
8
9
with hydrogen selenide generated from the reaction of
12
13
aldehydes or from alkyl chlorides and acyl chlorides,
respectively. Although Sonoda’s method is relatively
Al
2 3
Se and water gave diselenides in the presence of
organic base triethylamine. Diselenides were also syn-
12,13
convenient and can be easily manipulated,
the process
is subject to relatively high pressure of CO (0.5-3.0
(
1) (a) Liotta, D.; Monahan, R., III. Science 1986, 231, 356-361. (b)
MPa), high temperature (120 °C), and long reaction times
Krief, A. In Comprehensive Organometallic Chemistry; Abel, E. W.,
Stone, F. G. A., Wilkinson, G., Mckillop, A., Eds.; Pergamon: Oxford,
(e.g., 24 h), and when aromatic ketones ArC(dO)R′ were
1
995; Vol. II, pp 516-569. (c) Organoselenium Chemistry-A practical
Approach; Back., T. G., Ed.; Oxford University Press: Oxford, 1999.
d) Topics in Current Chemistry; Wirth, T., Ed.; Springer: Berlin, 2000;
Vol. 208.
2
used as the substrates, only reduction products ArCH R′
instead of diselenides were obtained.
14
(
In the course of our ongoing studies on selenium-
catalyzed reductive carbonylation of nitroaromatic com-
pounds with carbon monoxide,15 we have developed new
(2) (a) Gladysz, J .; Hornby, J .; Garbe, J . E. J . Org. Chem. 1978, 43,
1
6
2
1
204-1207. (b) Syper, L.; Mlochowshi, J . Tetrahedron 1988, 44, 6119-
130. (c) Thompson, D. P.; Boudjouk, P. J . Org. Chem. 1988, 53, 2109-
112. (d) Li, J . Q.; Bao, W. L.; Lue, P.; Zhou, X. J . Synth. Commun.
991, 21, 799-806. (e) Wang, J . X.; Cui, W.; Hu, Y. J . Chem. Soc.,
Perkin Trans. 1 1994, 2341-2343. (f) Krief, A.; Derock, M. Tetrahedron
Lett. 2003, 43, 3083-3086.
(10) (a) Lewicki, J . W.; G u¨ nther, W. H. H.; Chu, J . Y. C., J . C. S.
Chem. Commun. 1976, 552. (b) Lewicki, J . W.; G u¨ nther, W. H. H.; Chu,
J . Y. C. J . Org. Chem. 1978, 43, 2672-2676.
(3) (a) Krief, A.; Delmotte, C.; Dumont, W. Tetrahedron 1997, 53,
1
2147-12158. (b) Krief, A. Tetrahedron Lett. 2002, 43, 3083-3086.
(11) Huang, Z, Z.; Liu, F. Y.; Du, J . X.; Huang, X. Org. Prep. Proced.
Int. 1995, 27, 492-494.
(c) Krief, A.; Dumont, W.; Delmotte, C. Angew. Chem., Int. Ed. 2000,
3
9, 1669-1672.
(12) Nishiyama, Y.; Hamanaka, S.; Ogawa, A.; Murai, S.; Sonoda,
N. Synth. Commun. 1986, 16, 1059-1067.
(
4) (a) Salama, P.; Bernard, C. Tetrahedron Lett. 1995, 36, 5711-
5
7
714. (b) Salama, P.; Bernard, C. Tetrahedron Lett. 1998, 39, 745-
48.
(13) Nishiyama, Y.; Katsuura, A.; Negoro, A.; Hamanaka, S.;
Miyoshi, N.; Yamana, Y.; Ogawa, A.; Sonoda, N. J . Org. Chem. 1991,
56, 3776-3780.
(
5) Prabhu, K.; Chandrasekaran, S. Chem. Commun. 1997, 1021-
1
022.
(14) Nishiyama, Y.; Hamanaka, S.; Ogawa, A.; Kambe, N.; Sonoda,
N. J . Org. Chem. 1988, 53, 1326-1329.
(6) Krief, A.; De Mahieu, A. F.; Dumont, W.; Trabelsi, M. Synthesis
1
988, 131-133.
(15) (a) Yang, Y.; Lu, S. W. Tetrahedron Lett. 1999, 40, 4845-4846.
(b) Mei, J . T.; Yang, Y.; Xue, Y.; Lu, S. W. J . Mol. Catal. Catal. A:
Chem. 2003, 191, 135-139. (c) Ling, G.; Chen, J . Z.; Lu, S. W. J . Mol.
Catal. A: Chem. 2003, 202, 23-29. (d) Chen, J . Z.; Ling, G.; Lu, S. W.
Eur. J . Org. Chem. 2003, 17, 3446-3453.
(7) Krief, A.; Van Wemmel, T.; Redon, M.; Dumont, W.; Delmotte,
C. Angew. Chem., Int. Ed. 1999, 38, 2245-2247.
(
(
8) Margolis, D. S.; Pittman, R. W. J . Chem. Soc. 1957, 799-805.
9) Cohen, V. I. J . Org. Chem. 1977, 42, 510-511.
1
0.1021/jo049733i CCC: $27.50 © 2004 American Chemical Society
Published on Web 05/20/2004
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J . Org. Chem. 2004, 69, 4520-4523