Ruthenium(III) Chloride Catalyzed Efficient Synthesis of
Unsymmetrical Diorganyl Selenides via Cleavage of Dibenzyl and
Diphenyl Diselenides in the Presence of Zinc
Xiaodan Zhao,† Zhengkun Yu,*,† Shenggang Yan,‡ Sizhong Wu,† Ren Liu,† Wei He,† and
Liandi Wang†
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road,
Dalian, Liaoning 116023, P. R. China, and The Department of Chemistry,
Dalian University of Technology, Dalian, Liaoning 116024, P. R. China
Received May 21, 2005
An efficient one-pot route to unsymmetrical diorganyl selenides has been developed by ruthenium-
(III) chloride catalyzed reactions of dibenzyl or diphenyl diselenides with alkyl halides in the
presence of zinc. Organic iodides, bromides, and activated chlorides underwent the reactions
efficiently. Unreactive organic chlorides also underwent the same type of selenation with sodium
bromide as the additive.
Introduction
conditions for chemical cleavage of Se-Se bonds. Direct
nickel(II) bromide catalyzed coupling of a diaryl disele-
nide with an iodoaryl compound was realized in the
presence of a polymer-supported borohydride.3 Using a
bimetallic (Sn(II)/Cu(II)) system, reactions of reactive
organic bromides, i.e., allyl, propargyl, benzyl, and alky-
nyl bromides, with diorganyl diselenides gave unsym-
metrical monoselenides.4 Iodine-catalyzed reactions of
diphenyl diselenide with organic halides in the presence
of stoichiometric amount of lanthanum metal afforded
unsymmetrical phenylselenides.5 Indium(I) iodide pro-
moted formation of diorganyl selenides was achieved by
cleavage of diaryl diselenides and subsequent condensa-
tion with reactive alkyl or acyl chlorides.6 In the presence
of magnesium, copper(I)-catalyzed reactions of diphenyl
diselenide with aryl iodides afforded unsymmetrical
diaryl monoselenides.7 Palladium(0)-promoted cleavage
of diphenyl diselenide was also reported for phenylsel-
enation.8 Recently, a Zn/AlCl3 (4.6/2.0 equiv ratio) system
was employed to synthesize selenol esters by the reac-
tions of diphenyl and dibenzyl diselenides with acid
Organic selenides have been used as versatile reagents
in organic synthesis and catalysis.1 Cleavage of Se-Se
bonds, especially cleavage of diphenyl or other diaryl
diselenides, has recently received much effort for prepa-
ration of unsymmetrical diorganyl selenides (RSeR′).
Chemical cleavage of Se-Se bonds in diaryl diselenides
were realized with reducing agents such as NaBH4,
Na/NH3, Bu3SnH, LiAlH4, etc.2 However, catalytic pro-
cedures are considered more applicable for preparation
of functional unsymmetrical diorganyl selenides because
many functional groups cannot withstand the harsh
* To whom correspondence should be addressed. Fax: (+86)-411-
8437-9227.
† Dalian Institute of Chemical Physics.
‡ Dalian University of Technology.
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10.1021/jo051015o CCC: $30.25 © 2005 American Chemical Society
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