SCHEME 1. Synthesis of Vinyl Selenides and Sulfides
Indium(I) Iodide Promoted Cleavage of Diphenyl
Diselenide and Disulfide and Subsequent
Palladium(0)-Catalyzed Condensation with
Vinylic Bromides. A Simple One-Pot Synthesis of
Vinylic Selenides and Sulfides
addition to alkyl halides3a,b and activated alkenes.3c,d We also
observed during this study that vinylic halides remained inert
in this indium(I)-mediated selenate or thiolate condensation.
Further investigations now revealed that the presence of a
catalytic amount of Pd(0) derivatives in the reaction mixture
efficiently drives the condensation leading to the synthesis of
vinyl selenides and sulfides in one pot (Scheme 1), and the
results are reported here.
Brindaban C. Ranu,* Kalicharan Chattopadhyay, and
Subhash Banerjee
Department of Organic Chemistry, Indian Association for the
CultiVation of Science, JadaVpur, Kolkata 700 032, India
Organic selenides, in general, are of considerable interest in
academia as well as in industry because of their wide involve-
ment in organic synthesis4a and their useful biological activities.4b
Among various organoselenium compounds, vinylic selenides
are very useful intermediates,5a particularly in the synthesis of
carbonyl compounds5b and for the stereoselective preparation
of functionalized alkenes.5 As vinyl selenides are not very easy
to obtain, only a limited number of methods are available for
their synthesis,6 and in general, these are based on three general
approaches, namely, hydroselenation of alkynes,6a,b Wittig
olefination,6c and direct nucleophilic substitution of vinylic
halides.6d Although these procedures are quite satisfactory, one
serious limitation is in the accomplishment of one single
stereoisomer of the product as all of the methods,6 particularly
hydroselenation of alkynes and Wittig olefination strategies, lead
to formation of mixture of stereoisomers in varying proportions
(50:50-80:20). In addition, the long reaction time (12-48 h)6a,b
and higher temperature6d required for most of these methods
constitute practical disadvantages. On the other hand, vinylic
sulfides also have considerable synthetic utility in organic
chemistry,7 and similar protocols are used for their synthesis
too.8 Thus, considering the importance of these molecules, a
milder, more stereoselective, and convenient methodology is
highly desirable.
ReceiVed October 5, 2005
Diphenyl diselenide (and disulfide) undergo facile reaction
with indium(I) iodide and the corresponding intermediate
complex condenses in situ with a variety of substituted vinyl
bromides in the presence of a catalytic amount of tetrakis-
(triphenylphosphine)palladium(0) [Pd(PPh3)4] in THF at
room temperature to produce vinylic selenides and sulfides
in good yields. The conversion of (E)-vinyl bromides is
remarkably stereoselective giving (E)-vinyl selenides
(and sulpfides) whereas the stereoselectivity in reaction of
(Z)-vinyl bromides is not very good.
During the past decade, indium metal and its trihalides have
been demonstrated to be potential reagents for carbon-carbon
bond formation, rearrangements, reductions, and other useful
chemical transformations.1 This led to considerable current
interest to search for newer indium derivatives for novel
reactions. As a part of our interest and intense involvement in
this area during the past few years,1e,2 we recently undertook
an investigation to explore the application of indium(I) iodide
among others and discovered the facile cleavage of diorganyl
selenides and sulfides by this indium derivative and subsequent
The experimental procedure for this reaction is very simple.
A mixture of a substituted vinyl bromide, diphenyl diselenide
(3) (a) Ranu, B. C.; Mandal, T.; Samanta, S. Org. Lett. 2003, 5, 1439.
(b) Ranu, B. C.; Mandal, T. J. Org. Chem. 2004, 69, 5793. (c) Ranu, B.
C.; Mandal, T. Synlett 2004, 1239. (d) Ranu, B. C.; Das, A. Tetrahedron
Lett. 2004, 45, 6875.
(4) (a) Orgnoselenium Chemistry, Topics in Current Chemistry 208;
Wirth, T., Ed.; Springer-Verlag: Heidelberg, 2000. (b) Mugesh, G.; du Mont,
W.-W.; Sies, H. Chem. ReV. 2001, 101, 2125.
(5) (a) Comasseto, J. V. J. Organomet. Chem. 1983, 253, 131. (b)
Comasseto, J. V.; Petragnani, N. J. Organomet. Chem. 1978, 152, 295. (c)
Comasseto, J. V.; Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis
1997, 373.
(6) (a) Zeni, G.; Stracke, M. P.; Nogueira, C. W.; Braga, A. L.; Menezes,
P. H.; Stefani, H. A. Org. Lett. 2004, 6, 1135. (b) Comasseto, J. V.; Brandt,
C. A. Synthesis 1987, 146. (c) Silveira, C. C.; Begnini, M. L.; Boeck, P.;
Braga, A. L. Synthesis 1997, 221. (d) Cristau, H. J.; Chabaud, B.;
Labaudiniere, R.; Christol, H. J. Org. Chem. 1986, 51, 875.
(7) Cremlyn, R. J. An Introduction to Organo-sulfur Chemistry; Wiley
and Sons: New York, 1996.
(8) (a) Usugi, S.-i.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Org. Lett.
2004, 6, 601. (b) Bates, C. G.; Saejueng, P.; Doherty, M. Q.; Venkataraman,
D. Org. Lett. 2004, 6, 5005. (c) Carpita, A.; Rossi, R.; Scamuzzi, B.
Tetrahedron Lett. 1989, 30, 2699. (d) Murahashi, S.-I.; Yamamura, M.;
Yanagisawa, K.-i.; Mita, N.; Kondo, K. J. Org. Chem. 1979, 44, 2408. (e)
Kondo, T.; Mitsudo, T.-a. Chem. ReV. 2000, 100, 3205.
(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, 2347. (f) Babu, G.; Perumal, P. T. Aldrichim.
Acta 2000, 33, 16. (g) Podelech, J.; Maier, T. C. Synthesis 2003, 633. (h)
Nair, V.; Ros, S.; Jayan, C. N.; Pillai, B. S. Tetrahedron 2004, 68, 1959.
(2) (a) Ranu, B. C.; Hajra, A.; Jana, U. J. Org. Chem. 2000, 65, 6270.
(b) Ranu, B. C.; Hajra, A.; Jana, U. Tetrahedron Lett. 2000, 41, 531. (c)
Ranu, B. C.; Samanta, S.; Hajra, A. Synlett 2002, 987. (d) Ranu, B. C.;
Das, A.; Samanta, S. Synlett 2002, 727. (e) Ranu, B. C.; Dey, S. S.; Hajra,
A. Tetrahedron 2002, 58, 2529. (f) Ranu, B. C.; Hajra, A.; Dey, S. S.;
Jana, U. Tetrahedron 2003, 59, 813. (g) Ranu, B. C.; Samanta, S. J. Org.
Chem. 2003, 68, 7130. (h) Ranu, B. C.; Das, A.; Hajra, A. Synthesis 2003,
1012. (i) Ranu, B. C.; Samanta, S. Tetrahedron 2003, 59, 7901. (j) Ranu,
B. C.; Jana, R.; Samanta, S. AdV. Synth. Catal. 2004, 346, 446. (k) Ranu,
B. C.; Das, A. AdV. Synth. Catal. 2005, 347, 712.
10.1021/jo052087i CCC: $33.50 © 2006 American Chemical Society
Published on Web 12/02/2005
J. Org. Chem. 2006, 71, 423-425
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