Indium(I) iodide-mediated cleavage of diphenyl diselenide. An efficient one-pot procedure for the synthesis of unsymmetrical diorganyl selenides

Article abstract of DOI:10.1021/ol034178c

(Matrix presented) A simple and efficient procedure has been developed for the synthesis of unsymmetrical diorganyl selenides through a one-pot indium(I) iodide-mediated reaction of alkyl halide and diphenyl diselenide in methylene chloride at room temperature.

Full text of DOI:10.1021/ol034178c

ORGANIC
LETTERS
2003
Vol. 5, No. 9
1439-1441
Indium(I) Iodide-Mediated Cleavage of
Diphenyl Diselenide. An Efficient
One-Pot Procedure for the Synthesis of
Unsymmetrical Diorganyl Selenides
Brindaban C. Ranu,* Tanmay Mandal, and Sampak Samanta
Department of Organic Chemistry, Indian Association for the CultiVation of Science,
JadaVpur, Calcutta 700 032, India
ocbcr@iacs.res.in
Received February 1, 2003
ABSTRACT
A simple and efficient procedure has been developed for the synthesis of unsymmetrical diorganyl selenides through a one-pot indium(I)
iodide-mediated reaction of alkyl halide and diphenyl diselenide in methylene chloride at room temperature.
Indium metal and its salts have been the subject of continued
interest because of their remarkable efficiency in various
synthetic operations.1 However, although the synthetic utili-
ties of indium metal and indium(III) derivatives have been
well demonstrated, indium(I) salt has been less explored.2
As a part of our interest in indium chemistry,1e,3 we have
initiated an investigation on the use of indium(I) iodide for
useful chemical transformations.
key intermediates in organic synthesis and use as a food
supplement.4 On the other hand, organoselenium compounds
are no longer systematically classified as toxic and, thus,
much effort has been devoted toward synthesis of these
compounds in recent times. Although quite a number of
procedures for the synthesis of organoselenium compounds
have already been published,5 most of them, with the
exception of a recent report,5b usually require the handling
of unstable reagents, strongly basic or acidic reaction
conditions, and two-step procedures. Hence, an efficient
procedure involving a one-step operation under neutral
conditions is in demand. We have discovered a very simple
reaction of alkyl halide and diphenyl diselenide mediated
by indium(I) iodide at room temperature to produce a series
of unsymmetrical diorganyl selenides (Scheme 1), and the
results are presented here.
Organic selenides are of considerable interest in academia
as well as in industry because of their wide involvement as
* Fax: 91-33-2473-2805.
(1) (a) Cintas, P. Synlett 1995, 1087. (b) Li, C.-J. Tetrahedron 1996, 52,
5643. (c) Li, C.-J.; Chan, T. H. Tetrahedron 1999, 55, 11149. (d) Chauhan,
K. K.; Frost, C. G. J. Chem. Soc., Perkin Trans. 1 2000, 3015. (e) Ranu,
B. C. Eur. J. Org. Chem. 2000, 2343.
(2) (a) Marshall, J. A.; Grant, C. M. J. Org. Chem. 1999, 64, 696. (b)
Ohno, H.; Hamaguchi, H.; Tanaka, T. Org. Lett. 2000, 2, 2161. (c) Nobrega,
J. A.; Goncalves, S. M. C.; Peppe, C. Tetrahedron Lett. 2000, 41, 5779;
2001, 42, 4745. (d) Barros, O. S. de R.; Lang, E. S.; Oliveira, C. A. F. de.;
Peppe, C.; Zeni, G. Tetrahedron Lett. 2002, 43, 7921.
(3) (a) Ranu, B. C.; Hajra, A.; Jana, U. J. Org. Chem. 2000, 65, 6270.
(b) Ranu, B. C.; Hajra, A. J. Chem. Soc., Perkin Trans. 1 2001, 355. (c)
Ranu, B. C.; Samanta, S.; Guchhait, S. K. J. Org. Chem. 2001, 66, 4102.
(d) Ranu, B. C.; Dutta, J.; Guchhait, S. K. J. Org. Chem. 2001, 66, 5624.
(e) Ranu, B. C.; Dutta, J.; Guchhait, S. K. Org. Lett. 2001, 3, 2603. (f)
Ranu, B. C.; Samanta, S.; Hajra, A. J. Org. Chem. 2001, 66, 7519. (g)
Ranu, B. C.; Samanta, S.; Guchhait, S. K. J. Org. Chem. 2001, 66, 4102.
(h) Ranu, B. C.; Samanta, S.; Hajra, A. Synlett 2002, 987. (i) Ranu B. C.;
Das, A.; Samanta, S. Synlett 2002, 727. (j) Ranu, B. C.; Dey, S. S.; Hajra,
A. Tetrahedron 2002, 58, 2529. (k) Ranu, B. C.; Samanta, S.; Das, A.
Tetrahedron Lett. 2002, 43, 5993. (l) Ranu, B. C.; Samanta, S. Tetrahedron
Lett. 2002, 43, 7405. (m) Ranu, B. C.; Hajra, A.; Dey, S. S.; Jana, U.
Tetrahedron 2003, 59, 813.
Scheme 1
A wide range of structurally diverse alkyl halides under-
went reaction with diphenyl diselenide by this procedure6
(4) (a) Krief, A.; Hevesi, L. In Organoselenium Chemistry; Springer-
Verlag: Berlin, 1988; Vol. 1. (b) Krief, A. In ComprehensiVe Organometallic
Chemistry; Trost, B. M., Eds.; Pergamon Press: Oxford, 1991; pp 85-192.
10.1021/ol034178c CCC: $25.00 © 2003 American Chemical Society
Published on Web 04/01/2003

reaction conditions are sufficiently mild to be used in the
presence of CO2R, Cl, OMe, and methylenedioxy moieties.
We speculate that the reaction is going through the
alkylation pathway of bis(phenylseleno)-iodo-indium(III), 1,
formed readily by reacting equimolar quantities of InI and
diphenyldiselenide2c with alkyl halides to give the corre-
sponding selenide (Scheme 2). The possibility of a radical
Table 1. Synthesis of Alkyl Phenyl Selenides
Scheme 2
pathway through indium(I)-mediated cleavage of the alkyl
halide followed by addition to diphenyl diselenide is not
favored, as this procedure does not allow any reaction with
methyl acrylate and no dimerization product was found
during formation of phenyl selenobenzoate (entry 20) by
treatment of diphenyl diselenide with benzoyl chloride. The
isolation of only the R-addition product from the reaction
of crotyl bromide (entry 18) also supports the alkylation
pathway depicted in Scheme 2.
In general, the present procedure provides a relatively fast
(5-60 min), clean, and high-yielding (83-97%) reaction
compared to other methods.5 A recent report5b using diphenyl
diselenide in the presence of lanthanum metal and I2
demonstrates virtually no reaction with tertiary alkyl halide
and low yield (43% by GC) with benzoyl chloride. However,
our procedure does not find any difficulty in coupling with
tertiary alkyl bromide (entry 19) and reasonably good yields
(isolated) are obtained with benzoyl chloride (72%) (entry
20) and acetyl chloride (52%) (entry 21).
To conclude, an efficient one-pot procedure for the
synthesis of alkyl phenyl selenides has been developed
through the indium(I)-mediated reaction of diphenyl dis-
elenides with a variety of alkyl halides. This method offers
significant improvements with regard to operational simplic-
ity, reaction time, reaction conditions (room temperature and
neutral medium), general applicability (coupling with tertiary
alkyl halide and acyl chlorides), and high isolated yields of
products, and thus it provides a better and practical alternative
to the existing procedures5 for the synthesis of diorganyl
selenides. Moreover, this procedure demonstrates the syn-
a Yields refer to those of pure isolated products characterized by IR and
1H and 13C NMR spectroscopic data.
to provide the corresponding alkyl phenyl selenides in
excellent yields. The results are summarized in Table 1.
Although the reactions of benzylic (entries 1-8) and allylic
(entries 14-18) halides are more facile, other alkyl halides
(entries 9-12) are also converted to the corresponding
selenides over a longer reaction period. On the other hand,
in general, bromides and iodides react faster than chlorides.
Secondary (entries 8, 13) and tertiary (entry 19) bromides
also undergo clean reactions. More significantly, acyl
chlorides (entries 20, 21) take part in this reaction to furnish
the respective phenyl selenobenzoates. However, aryl halides
and vinyl halides remained inactive in this operation. The
(6) Representative Experimental Procedure (Entry 2). To a stirred
solution of benzyl bromide (171 mg, 1 mmol) and diphenyl diselenide (156
mg, 0.5 mmol) in dry methylene chloride (2 mL) was added indium(I) iodide
(121 mg, 0.5 mmol) at room temperature under nitrogen. The reaction
mixture was stirred for another 10 min (checked by TLC) and quenched
with a few drops of H2O. The mixture was then extracted with ether (3 ×
15 mL), and the combined ether extract was washed with brine, dried (Na2-
SO4), and evaporated to leave the crude product. The crude product was
purified by column chromatography over silica gel (hexane/ether 95:5) to
furnish the pure benzyl phenyl selenide as a yellow liquid (232 mg, 94%),
whose IR and 1H and 13C NMR spectral data are identical to those reported.5b
This procedure was followed for the synthesis of all alkyl phenyl selenides
listed in Table 1. The known compounds were identified by comparison of
their spectral data with that reported,5b and the new compounds were
(5) (a) Krief, A.; Derock, M. Tetrahedron Lett. 2002, 43, 3083 and
references therein. (b) Nishino, T.; Okada, M.; Kuroki, T.; Watanabe, T.;
Nishiyama, Y.; Sonoda, N. J. Org. Chem. 2002, 67, 8696 and references
therein.
1
properly characterized by their IR, H NMR, and 13C NMR spectroscopic
data.
1440
Org. Lett., Vol. 5, No. 9, 2003

thetic potential of indium(I) iodide and provides great
promise toward other useful applications.
Supporting Information Available: Spectral (IR and 1H
and 13C NMR) data of the products (listed in entries 4-9,
12-14, 19, 21, Table 1) not reported earlier. This material
is available free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. We are pleased to acknowledge the
financial support from CSIR, New Delhi [Grant 01(1739)/
02] for this investigation. T.M. and S.S. are also thankful to
CSIR for their fellowships.
OL034178C
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