In conclusion, we demonstrated the Tishchenko reaction
catalyzed by a nickel(0) complex, in which the oxidative
cyclization of two aldehyde molecules with nickel(0) is an
important key reaction step. The reaction can be applied to a
variety of aliphatic aldehydes (11, 21, 31) and aromatic
aldehydes. The reaction rate constant is zero-order in the
aldehyde concentration. The observed primary kinetic isotope
effect suggests that the rate-determining step is b-hydrogen
elimination or reductive elimination. Thus, this reaction shows
the high potential of the nickel catalyst for the Tishchenko
reaction.
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6 The molecular structure of C1 was assumed to be a cubic tetra-
meric structure as shown in Scheme 1 by X-ray crystallography.
However, we could not accurately obtain its structure due to the
disorder of the positions of oxygen and nickel and the disorder of
the PCy3 moiety.
This work was supported by a Grant-in-Aid for Scientific
Research (No. 21245028) and Encouragement for Young
Scientists (B) (No. 21750102) from MEXT.
Notes and references
z General experimental procedures of Ni(0)/IPrCl-catalyzed Tishchenko
reaction (Table 2): to a solution of Ni(cod)2 (11.0 mg, 0.040 mmol) and
IPrCl (18.3 mg, 0.040 mmol) in 2 mL of toluene was added the
aldehyde (4 mmol) under an inert atmosphere at 23 1C. The reaction
mixture was heated at 60 1C or 80 1C for 1–24 h. The reaction
was monitored by GC analysis. GC yields were determined using
pentadecane as an internal standard. The product was isolated by a
silica gel chromatography.
7 The formation of C1 in nickel-catalyzed reactions employing
carbonyl compounds or alcohols was observed. Thus, the complex
C1 would be a dead-end complex in catalytic reactions of carbonyls
compounds or alcohols.
8 More than 30 patents have been reported for the use of 11 in
cosmetics during the past 10 years.
9 A limited number of catalysts can catalyze the Tishchenko reaction
of enolizable aldehydes: T. Ooi, K. Ohmatsu, K. Sasaki, T. Miura
and K. Maruoka, Tetrahedron Lett., 2003, 44, 3191.
1 (a) L. Kurti and B. Czako, in Strategic Applications of Named
´
¨
10 Resonances carbonyl carbon and hydeorgen of Z2-aldehyde are
shifted significantly upfield: Y. H. Huang and J. A. Gladysz,
J. Chem. Educ., 1988, 65, 298, and references therein.
Reactions in Organic Synthesis, Elsevier Academic Press,
Burlington, 2005, pp. 456–457; (b) T. Seki, T. Nakajo and
M. Onaka, Chem. Lett., 2006, 35, 824–829, and references therein.
2 (a) F. Kakiuchi and S. Murai, Activation of C–H Bonds: Catalytic
Reactions, in Topics in Organometallic Chemistry. Activation of
Unreactive Bonds and Organic Synthesis, ed. S. Murai, Springer,
New York, 1999, vol. 3, ch. 3; (b) C. H. Jun, E.-A. Jo and
J.-W. Park, Eur. J. Org. Chem., 2007, 1869; (c) Decarbonylation
can be suppressed in an intramolecular reaction: S. H. Bergens,
D. P. Fairlie and B. Bosnich, Organometallics, 1990, 9, 566.
3 Isolated examples of hetero-nickelacycles proposed as a reaction
intermediate: (a) S. Ogoshi, M. Oka and H. Kurosawa,
11 For details, see ESIw.
12 The value of the observed kinetic effect is plausible for either b-H
elimination or reductive elimination. (a) E. J. Alexanian and
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This journal is The Royal Society of Chemistry 2010
3356 | Chem. Commun., 2010, 46, 3354–3356