R. Singha et al. / Tetrahedron Letters 53 (2012) 6531–6534
6533
Br
Br
route for the synthesis of 1,2,3,4-tetra phenyl naphthalene which
is a key material for the development of organic light emitting
devices,16 via palladium-catalyzed Suzuki reaction17 with an excel-
lent yield (Scheme 4).
In summary, we have developed a new and efficient methodol-
ogy for the regioselective cyclization of simple aromatic diynes to
multi-substituted 1,2,3-tribromo naphthalenes under simple reac-
tion conditions.18,19 We have also successfully applied our method-
ology for the synthesis of the important molecule, 1,2,3,4-tetraaryl
naphthalene, using known palladium-catalyzed reaction.
Br2
Br2
Br
Br
Br+
B
A
Ph
Ph
Br
Br
Ph
Br
Br
Br
Br
- H
H
Ph
2a
C
Scheme 2. Plausible rationale for the product formation.
Acknowledgment
We gratefully acknowledge D.S.T. for providing funds for the
project and creating 400 MHz NMR facility under the IRPHA pro-
gram. R. S. thanks CSIR, New Delhi for the fellowship.
Supplementary data
Supplementary data associated with this article can be found,
References and notes
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Scheme 3. ORTEP structure of compound 2a.
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Br
Ph
Ph
Br
Br
Ph
Ph
PhB(OH)2
Pd(PPh3)4, Et3N
DMF, 120 oC, 12 h
87%
2a
3
Ph
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Scheme 4. Synthesis of 1,2,3,4-tetra phenyl naphthalene.
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18. General procedure for the synthesis of 1,2,3-tribromo naphthalenes: 1,4-diaryl-
buta-1,3-diyne (0.5 mmol) and CH2Cl2 (2 mL) were taken in a round bottom
Thus the other isomer is not isolable (Table 1, entry 6). A plausible
mechanism for the formation of the products 2a–f is shown in
Scheme 2. At first dibromination occurred at one of the triple
bonds and the intermediate A was formed. The next bromination
on another triple bond provided a cyclic bromonium ion interme-
diate B. The intermediate B then underwent 6-endo-dig cyclization
to produce a cationic intermediate C which upon deprotonation
afforded the desired compound 1,2,3-tribromo naphthalene.
Structure of the compound 1,2,3-tribromo-4-phenyl naphtha-
lene (2a) was confirmed from its crystal structure (Scheme 3)
and ratified from its derivative 1,2,3,4-tetraphenyl naphthalene
as described in Scheme 4.
Halogenated naphthalenes are important intermediates in or-
ganic chemistry mainly due to the recent developments of transi-
tion metal catalyzed reactions. Here, we have shown an efficient