4
Tetrahedron
Supplementary Material
3000
2000
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0
1
Supplementary data (characterization data and H NMR, 13C
NMR spectra of all compounds listed in Tables 2, 3, and 4,
Schemes 2 and 4) associated with this article can be found, in the
online version, at
References and notes
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100
200
300
400
500
Magnetic Field Strength(G)
Fig. 1. EPR study of the reaction
Thus these observations suggest that the reaction follows a
radical pathway. Based on these observations the following
reaction mechanism is proposed. Aniline is nitrosated by
tBuONO to produce the diazonium unit (A) which successfully
produced the corresponding aryl radical (B) in the presence of Fe
(0). Then this aryl radical reacts with diphenyl diselenide to
produce the corresponding diaryl selenide (Scheme 5).
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Scheme 5. Probable mechanistic pathway
In conclusion, we have developed an efficient and general
method for the synthesis of aryl/heteroaryl sulfides, selenides and
tellurides from aryl/heteroaryl amines via in situ diazotization
using tBuONO and subsequent reaction with diaryl
dichalcogenides in the presence of Fe(0) nanoparticles by a
uniform protocol. This procedure avoids the isolation and
handling of hazardous diazonium salt and the reaction was
performed in one pot. This reaction is compatible with a broad
range of functionalities and heteroaryl amines which are not
often addressed.7-9,12 The reaction proceeds by a radical pathway
and a rationale mechanism has been outlined. The generation of
aryl radical by the interaction of diazonium moiety with Fe(0)
nanoparticle is not reported earlier and is of potential for further
applications.
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Acknowledgments
We gratefully acknowledge financial support from DST, Govt.
of India, New Delhi with an award of the J. C Bose fellowship
to B.C.R. (Grant no. SR/S2/JCB-11/2008) and Indian
National Science Academy, New Delhi for an offer of INSA
Sr. Scientist position to B.C.R. Finally, S.P. and P.M. thank
CSIR, New Delhi for their Fellowships.