temperature (100-150 °C), and long reaction time (∼24 h).
Especially, C-S cross-coupling reactions with volatile thiols,
such as n-propyl thiol and isopropyl thiol, were difficult.
Therefore, the development of efficient catalytic systems to
overcome these difficulties is still needed. Recently, we reported
novel and efficient Pd-catalyzed C-C cross-coupling reactions
using allylindiums, allenylindiums, tri(organo)indiums, and
tetra(organo)indates on the basis of the intriguing chemical
properties of indium metal.9 However, C-S cross-coupling
reactions with organoindium reagents have not been reported
despite one of the principal methods of forming C-heteroatom
bonds. These results have led us to investigate the participation
of organoindium reagents in C-S cross-coupling reactions. In
continuation of our studies directed toward the development of
efficient indium-mediated reactions, we described herein indium
tri(organothiolate), derived from a variety of volatile as well as
nonvolatile thiols, as the nucleophilic cross-coupling partners
in Pd-catalyzed C-S cross-coupling reactions. Also, their
applications to sequential one-pot processes in combination with
allyl- and allenylindiums led to the formation of functionalized
sulfides and bis(sulfides).
Palladium-Catalyzed Carbon-Sulfur
Cross-Coupling Reactions with Indium
Tri(organothiolate) and Its Application to
Sequential One-Pot Processes
Jae-Young Lee and Phil Ho Lee*
National Research Laboratory for Catalytic Organic
Reaction, Department of Chemistry, and Institute for
Molecular Science and Fusion Technology, Kangwon
National UniVersity, Chuncheon 200-701, Republic of Korea
ReceiVed June 17, 2008
First, the catalytic activity of several palladium complexes
was examined in the reaction of 2-bromonaphthalene (2a) with
indium tri(benzenethiolate) (1a),10 which was produced from
the reaction of indium with phenyl disulfide. The results are
summarized in Table 1. Among the catalysts examined, 4 mol
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It was found that indium tri(organothiolate) is an effective
nucleophilic coupling partner in Pd-catalyzed C-S cross-
coupling reactions to produce the functionalized sulfides in
excellent yields with high atom efficiency and complete
regio- and chemoselectivity. The present method was ef-
ficiently applied to the sequential one-pot processes com-
posed of selective double C-S cross-coupling reactions and
addition of allylindium or allenylindium to aldedyde to give
the functionalized sulfides and bis(sulfides).
(3) (a) Zhang, Y.; Ngeow, K. C.; Ying, J. Y. Org. Lett. 2007, 9, 3495. (b)
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The sulfide group is a key motif in chemistry and biology.
Because of the characteristic features of the C-S bond as a
function of biological, pharmaceutical, and material sciences,1
transition metal, such as Pd,2 Ni,3 Cu,4 Co,5 Rh,6 Pt,7 and Fe,8
catalyzed C-S cross-coupling reactions have received much
attention and been studied by means of the development of new
catalytic systems and appropriate reagents. Especially, the
synthesis of sulfides catalyzed by palladium has shaped up by
employment of the newly designed phosphine ligand, which
creates a long-lived catalyst.2a,c Although interesting C-S cross-
coupling reactions have been reported, they usually required
harsh conditions such as excess use of thiol, high reaction
(1) (a) Liu, G.; Huth, T. R.; Olejniczak, E. T.; Mendoza, R.; Devries, P.;
Leitza, S.; Reilly, E. B.; Okasinski, G. F.; Fesik, S. W.; Von Geldern, T. W.
J. Med. Chem. 2001, 44, 1202. (b) Wang, W.; Chackalamannil, S.; Chang, W.;
Greenlee, W.; Ruperto, V.; Duffy, R. A.; MacQuade, R.; Lachowicz, J. E. Bioorg.
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Schmittling, E. A.; Palkowitz, J. A.; Smith, W. J., III J. Org. Chem. 1998, 63,
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10.1021/jo801169h CCC: $40.75
Published on Web 08/20/2008
2008 American Chemical Society
J. Org. Chem. 2008, 73, 7413–7416 7413