Organic Letters
Letter
Ed. 2012, 51, 2943. (e) Li, H.; Shangguan, X.; Zhang, Z.; Huang, S.;
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intermediate I, which reacts with NBS to form II. Further II
reacts with TBAB to afford the dibromide III (which was
isolated). Under heating conditions, III loses HBr to furnish the
corresponding vinyl halide. Further, the reaction of preformed
diazo compound (1-(1-diazoethyl)-4-methoxybenzene) under
optimal conditions has resulted in the formation of correspond-
ing vinyl bromide 3c in 51% indicating the intermediacy of diazo
species (see SI-Scheme 5, Supporting Information). In the
reaction of CNBr−TBAB, with the bromine radical reacts with 2
to form IV which upon extrusion of N2 followed by migration of
tosyl group forms the stable intermediate V, which was isolated in
an independent experiment. The tosyl group migration in these
reactions has been further confirmed by performing a mixed
reaction of two sulfonyl hydrazine derivatives with CNBr−TBAB
under the optimal conditions, which yielded a mixture of sulfone
products (see SI-Scheme 6, Supporting Information).15 Based on
this information, we believe that the intermediate V undergoes
dehydrohalogenation to furnish the corresponding vinyl
sulfones, which was also isolated in an independent experiment
(see SI-Scheme 7, Supporting Information). A further study to
follow the formation of alkynes is underway in our laboratory.
It has been demonstrated that it is possible to trap the diazo
species in an intermolecular fashion by attack of two independent
ion species in tandem at the carbene center to install an
electrophile and a nucleophile on the same carbon. This process
has led to the formation of a gem-dihalide intermediate followed
by vinyl halides. Further, the reaction of tosylhydrazone with
CNBr and aliphatic quarternary ammonium salts has resulted in
the formation of vinyl sufones, in which the migration of a tosyl
group has been witnessed for the first time. A novel avenue for
synthesizing alkynes from hydrazones as well as ketones has thus
been revealed.
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ASSOCIATED CONTENT
* Supporting Information
Experimental procedures, characterization data, and spectra for
all compounds. This material is available free of charge via the
■
S
AUTHOR INFORMATION
Corresponding Author
■
(12) (a) Nair, V.; Augustine, A.; Suja, T. D. Synthesis 2002, 2259.
(b) Xu, W. M.; Tang, E.; Huang, X. Synthesis 2004, 2094. (c) Dez, D.;
Garca, P.; Marcos, I. S.; Garrido, N. M.; Basabe, P.; Broughton, H. B.;
Urones, J. G. Tetrahedron 2005, 61, 699. (d) Guan, Z.-H.; Zuo, W.;
Zhao, L.-B.; Ren, Z.-H.; Liang, Y.-M. Synthesis 2007, 1465. (e) Signore,
G.; Malanga, C.; Menicagli, R. Tetrahedron 2008, 64, 11218. (f) Das, B.;
Lingaiah, M.; Damodar, K.; Bhunia, N. Synthesis 2011, 2941. (g) Liang,
S.; Zhang, R.-Y.; Wang, G.; Chen, S.-Y.; Yu, X.-Q. Eur. J. Org. Chem.
2013, 7050. (h) Taniguchi, N. Tetrahedron 2014, 70, 1984.
(13) See the Supporting Information for the proposed reaction
mechanism of 1,2-migration of the sulfone moiety (see SI-Scheme 8,
Supporting Information).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Indian Institute of Science and
RL Fine Chem. We are thankful to Dr. S. Raghothama (NRC,
IISc) and Dr. A. R. Ramesha (RL Fine Chem) for useful
discussions. D.P.O. thanks UGC, New Delhi, for a senior
research fellowship.
(14) Collins, K. D.; Glorius, F. Nat. Chem. 2013, 5, 597.
(15) See the Supporting Information for the mixed experiment and
proposed reaction mechanism. We are thankful to anonymous referees
for useful suggestions.
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