ChemComm
Communication
Table 4 Reactions of electrophiles with the arylmagnesiation intermediatea
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Electrophiles
E
Product
Yieldb (%)
I2
I
4aaa
4aab
84c/68d
78c/70d
PhCHO
CHPh(OH)
a
Reactions were carried out using 0.5 mmol diphenylacetylene (1a) and
0.6 mmol phenylmagnesium bromide (2a) in 2.0 mL solvent under N2
b
c
for 1 h, then the electrophile was added. Isolated yield. At 0 1C for a
d
further 3 h. At r.t. for a further 3 h.
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comparable to those obtained from the reactions catalysed by the
Fe(acac)3–iPr (iPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-yli-
dene) system,5c but with higher stereoselectivity.
Reactions of the intermediary alkenylmagnesium with other
electrophiles such as iodine and benzaldehyde give the corres-
ponding tetra-substituted alkenes with higher yield at 0 1C than
at r.t. (Table 4).
In summary, we have demonstrated a nickel-catalysed aryl-
magnesiation of diarylacetylenes and aryl(alkyl)acetylenes avoid-
ing the addition of any supporting ligands. The catalytic method
is mediated by NiCl2Á6H2O at r.t. and is applicable to a range of
substrates. It conveniently generates various tri-substituted
alkenes by subsequent hydrolysis with excellent yields and high
stereo- and regioselectivity. The process offers facile one-pot
access to multi-substituted olefins. We are currently exploring
the adoption of similar methods to construct other functional
unsaturated systems especially using complex electrophiles.
We acknowledge the National University of Singapore, the
Ministry of Education (WBS No: R-143-000-361-112) and the
Agency for Science, Technology and Research (A*Star) of Singapore
(WBS No: R-143-000-426-305) for financial support.
7 S. Cacchi, G. Fabrizi, A. Goggiamani and D. Persiani, Org. Lett., 2008,
10, 1597.
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J., 2010, 16, 7688; (d) B.-H. Tan, J. Dong and N. Yoshikai, Angew.
Chem., Int. Ed., 2012, 51, 9610; (e) M. Corpet and C. Gosmini, Chem.
Commun., 2012, 48, 11561.
Notes and references
1 (a) P. Knochel, in Comprehensive Organic Synthesis, ed. B. M. Trost,
I. Fleming and M. F. Semmelhack, Pergamon Press, New York, 1991,
vol. 4, ch. 4.4, pp. 865–911; (b) I. Marek and J. Normant, in Metal-
Catalysed Cross-Coupling Reactions, ed. F. Diederich and P. J. Stang,
Wiley-VCH, New York, 1998, pp. 271–337; (c) K. Fagnou and
M. Lautens, Chem. Rev., 2003, 103, 169; (d) C.-J. Li, Chem. Rev.,
9 F. Xue, J. Zhao and T. S. A. Hor, Dalton Trans., 2013, 42, 5150.
10 D. Xu, C. Lu and W. Chen, Tetrahedron, 2012, 68, 1466.
c
This journal is The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 10121--10123 10123