Journal of the American Chemical Society
COMMUNICATION
hydrogenation of 1,3-butadiene under the reaction conditions. The
large difference in reactivity between PCy3 and IPr is mostly caused by
the difference in the stability of the diazanickelacycle C. Thermolysis
of 24d for 24 h at 130 °C gave 1 in 48% yield. In contrast, the
corresponding IPr analogue (24e) was found to be too stable to
regenerate the azanickelacycle intermediate 23b.19
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In conclusion, we demonstrated the dehydrogenative [4 + 2]
cycloaddition of 1,3-butadienes with nitriles to give a variety of
pyridines catalyzed by nickel(0) complexes. The prepared pyri-
dines in this report were very difficult to prepare by [2 + 2 + 2]
cycloaddition reactions of alkynes with nitriles. Moreover, the
reaction can be applied to both di- and tricyano compounds.
These polypyridine derivatives were shown to be potentially
useful ligands to transition metal complexes. Moreover, the for-
mation of the expected intermediate and its molecular structure
were revealed by crystallography.
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’ ASSOCIATED CONTENT
S
Supporting Information. Detailed experimental proce-
b
ꢀ
dures, analytical and spectral data for all new compounds, and
crystallographic data (PDF/CIF) for 23b,23c,and24d.Thismaterial
(10) Ohashi, M.; Ikawa, M.; Ogoshi, S. Organometallics 2011, 30,
2765–2774.
(11) Ogoshi, S.; Tonomori, K.-i.; Oka, M.-a.; Kurosawa, H. J. Am.
Chem. Soc. 2006, 128, 7077–7086.
’ AUTHOR INFORMATION
(12) Ogoshi, S.; Oka, M.; Kurosawa, H. J. Am. Chem. Soc. 2004,
126, 11802–11803.
Corresponding Author
(13) Running the catalytic reaction under the o-xylene reflux condi-
tions, which would help drive off the H2 that is generated, could not
suppress the formation of the corresponding hydrogenated butene.
(14) (a) Yamamoto, Y.; Ogawa, R.; Itoh, K. J. Am. Chem. Soc. 2001,
123, 6189–6190. (b) Naiman, A.; Vollhardt, K. P. C. Angew. Chem., Int.
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’ ACKNOWLEDGMENT
This work was supported by Grants-in-Aid for Scientific
Research (No. 21245028) and for Scientific Research on In-
novative Areas “Molecular Activation Directed toward Straight-
forward Synthesis” (No. 23105546) from MEXT.
(15) NMR observation of the reaction revealed the formation of a
diazanickelacycle complex (24a) and trans-(PCy3)2Ni(CtN)(Ph) (25)
in 8 and 6%, respectively. Details are found in the Supporting Information.
(16) Oxidative addition of PhCN to Ni(0): (a) Atesin, T. A.; Li, T.;
Lachaize, S.; García, J. J.; Jones, W. D. Organometallics 2008, 27, 3811–3817.
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(17) Detailed procedures for 23c and 24d, including the results of
X-ray analysis, are found in the Supporting Information.
(18) The treatment of nickel compounds with carbon monoxide can
yield [Ni(CO)4] (extremely toxic) due to the addition of insufficient
amounts of ligands, careless handling, or an accident. The reaction
mixture must be handled within a well-ventilated fume hood.
(19) See Supporting Information for detail.
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