Journal of the American Chemical Society
COMMUNICATION
Tishchenko reaction of two aldehydes, and the study will
contribute to the further development of the environmentally
benign synthesis of esters.
(8) In the course of evaluating the scope of electron-deficient aryl
aldehydes, we carried out the crossed Tishcheko reaction of p-Cl- and
p-NO2-substituted benzaldehydes with CyCHO. However, the cross-
coupled esters were not obtained at all; precipitations were observed
instead, and we could not identify the products.
(9) For example, see: Vijayalakshmi, N.; Maitra, U. J. Org. Chem.
2006, 71, 768–774.
(10) Song-Hae, B.; Eun-Eai, K.; Sang-Ku, L.; Ji-Won, Y.; Hee-Sook,
J.; Lee-Yong, K.; Wi, K. Patent No.: US 7,192,981 B2.
’ ASSOCIATED CONTENT
S
Supporting Information. Full experimental details and
b
discussion of the optimization of reaction conditions, NMR
experiments, reaction mechanism, and spectra. This material is
(11) (a) Sakaki, S.; Kitaura, K.; Maruoka, K.; Ohkubo, K. Inorg.
Chem. 1983, 22, 104–108. (b) Delbecq, F.; Sautet, P. J. Am. Chem. Soc.
1992, 114, 2446–2455.
(12) For examples of a nickelacycle species proposed as a key
intermediate in the nickel-catalyzed coupling reaction employing an
aldehyde, see: (a) Sato, Y.; Takanashi, T.; Mori, M. Organometallics
1999, 18, 4893. (b) Amarasinghe, K. K. D.; Chowdhury, S. K.; Heeg, M. J.;
Montgomery, J. Organometallics 2001, 20, 370–372. (c) Mahandru, G. M.;
Skauge, A. R. L.; Chowdhury, S. K.; Amarasinghe, K. K. D.; Heeg, M. J.;
Montgomery, J. J. Am. Chem. Soc. 2003, 125, 13481–13485. (d) Ogoshi, S.;
Oka, M.; Kurosawa, H. J. Am. Chem. Soc. 2004, 126, 11802–11803. (e) Ng,
S. S.; Ho, C. Y.; Jamison, T. F. J. Am. Chem. Soc. 2006, 128, 11513–11528.
(f) Ogoshi, S.; Tonomori, K. I.; Oka, M. A.; Kurosawa, H. J. Am. Chem. Soc.
2006, 128, 7077–7086. (g) Ogoshi, S.; Arai, T.; Ohashi, M.; Kurosawa, H.
Chem. Commun. 2008, 1347–1349. (h) Baxter, R. D.; Montgomery, J.
J. Am. Chem. Soc. 2008, 130, 9662–9663. (i) McCarren, P. R.; Liu, P.;
Cheong, P. H. Y.; Jamison, T. F.; Houk, K. N. J. Am. Chem. Soc. 2009,
131, 6654–6655. (j) Ohashi, M.; Saijo, H.; Arai, T.; Ogoshi, S. Organome-
tallics 2010, 29, 6534–6540. For a review, see:Ogoshi, S. Yuki Gosei Kagaku
Kyokaishi 2009, 67, 507–516.
(13) For examples of an acylnickel species proposed as a key
intermediate in the nickel-catalyzed coupling reaction employing an
aldehyde, see: (a) Tsuda, T.; Kiyoi, T.; Saegusa, T. J. Org. Chem. 1990,
55, 2554–2558. (b) Taniguchi, H.; Ohmura, T.; Suginome, M. J. Am.
Chem. Soc. 2009, 131, 11298–11299.
(14) An example of a dioxanickelacycle derived from two carbonyl
compounds has been reported. See: Browning, J.; Green, M.; Stone,
F. G. A. J. Chem. Soc. A 1971, 453–457.
’ AUTHOR INFORMATION
Corresponding Author
’ ACKNOWLEDGMENT
This work was supported by Grants-in-Aid for Scientific
Research (21245028) and Encouragement for Young Scientists
(B) (21750102) and a Grant-in-Aid for Scientific Research on
Priority Areas “Advanced Molecular Transformations of Carbon
Resources” from MEXT. S.O. and M.O. acknowledge the NAGASE
Science and Technology Foundation and the Japan Petroleum
Institution, respectively, for the Grants for Research. Y.H. expresses
his special thanks for the Research Fellowship for Young Scientists
(JSPS) and the Global COE Program “Global Education and
Research Center for Bio-Environmental Chemistry” of Osaka
University. We also gratefully acknowledge a reviewer for valuable
comments and suggestions regarding the reaction mechanism.
’ REFERENCES
(1) Larock, R. C. Comprehensive Organic Transformations, 2nd ed.;
Wiley-VCH: Weinheim, Germany, 1999.
(2) (a) K€urti, L.; Czakꢀo, B. Strategic Applications of Named Reactions
in Organic Synthesis; Elsevier Academic Press: Burlington, MA, 2005. For
reviews, see:(b) T€orm€akangas, O. P.; Koskinen, A. M. P. Recent Res. Dev.
Org. Chem. 2001, 5, 225–255. (c) Seki, T.; Nakajo, T.; Onaka, M. Chem.
Lett. 2006, 35, 824–829.
(3) (a) Ogata, Y.; Kawasaki, A. Tetrahedron 1969, 25, 929–935. (b)
Seki, T.; Kabashima, H.; Akutsu, K.; Tachikawa, H.; Hattori, H. J. Catal.
2001, 204, 393–401. (c) Seki, T.; Hattori, H. Catal. Surv. Asia 2003,
7, 145–156. (d) Chen, Y.; Zhu, Z.; Zhang, J.; Shen, J.; Zhou, X. J.
Organomet. Chem. 2005, 690, 3783–3789. (e) Andrea, T.; Barnea, E.;
Eisen, M. S. J. Am. Chem. Soc. 2008, 130, 2454–2455. (f) Lin, A.; Day,
A. R. J. Am. Chem. Soc. 1952, 74, 5133–5135. (g) Morita, K.; Nishiyama,
Y.; Ishii, Y. Organometallics 1993, 12, 3748–3752.
(4) Recently, catalytic hydroacylations of ketones have been re-
ported. These are analogous to the Tishchenko reaction and give the
corresponding esters with good to excellent selectivity. See: (a) Hsu,
J. L.; Fang, J. M. J. Org. Chem. 2001, 66, 8573–8584. (b) Shen, Z.; Khan,
H. A.; Dong, V. M. J. Am. Chem. Soc. 2008, 130, 2916–2917. (c) Phan,
D. H. T.; Kim, B.; Dong, V. M. J. Am. Chem. Soc. 2009,
131, 15608–15609. (d) Omura, S.; Fukuyama, T.; Murakami, Y.;
Okamoto, H.; Ryu, I. Chem. Commun. 2009, 6741–6743. (e) Cronin,
L.; Manoni, F.; O’Connor, C. J.; Connon, S. J. Angew. Chem., Int. Ed.
2010, 49, 3045–3048.
(15) For an example of β-hydrogen elimination from an aldehyde
moiety in the oxanickelacycle, see ref 12g.
(16) Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic
Chemistry; University Science Books: Mill Valley, CA, 2006; pp
421ꢀ430.
(17) In ref 6, we could not conclude whether β-hydrogen elimina-
tion or reductive elimination is the rate-limiting step in the nickel-
catalyzed Tishchenko reaction. However, on the basis of the results of
this work, it can be assumed that reductive elimination is also the rate-
limiting step of the homocoupling reaction.
(18) Inverse kinetic isotope effects are often observed when the
hybrization changes from sp2 to sp3. See ref 16 and: Merrifield, J. H.; Lin,
G.; Kiel, W. A.; Gladysz, J. A. J. Am. Chem. Soc. 1983, 105, 5811.
(19) (a) Murahashi, S. I.; Naota, T.; Ito, K.; Maeda, Y.; Taki, H.
J. Org. Chem. 1987, 52, 4319–4327. (b) Bernard, K. A.; Atwood, J. D.
Organometallics 1988, 7, 235–236. (c) Bergens, S. H.; Fairlie, D. P.;
Bosnich, B. Organometallics 1990, 9, 566. (d) Barrio, P.; Esteruelas,
M. A.; O~nate, E. Organometallics 2004, 23, 1340–1348. (e) Tejel, C.;
Ciriano, M. A.; Passarelli, V. Chem.—Eur. J. 2011, 17, 91–95.
(20) We examined combinations of two different aliphatic or two
different aryl aldehydes, but it was difficult to prepare a single cross-
coupled ester selectively under the presented reaction conditions. For
example, the reaction of A1 with an equimolar amount of A4 in benzene
at ambient temperature in the presence of 10 mol% Ni(cod)2/IPr gave
A1A4, A4A1, A1A1, and A4A4 in 9, 34, 24, and 31% yield, respectively.
The cross-coupling reaction of two different aryl aldehydes was rather
selective. The reaction of B6 with an equimolar amount of B8 in benzene
at ambient temperature in the presence of 10 mol% Ni(cod)2/IMes gave
B6B8, B8B6, B6B6, and B8B8 in 53, 1, 2, and 17% yield, respectively.
(5) The NHCs employed in this manuscript were the following: 1,3-
bis(2,6-diisopropylphenyl)-4,5-dichloroimidazol-2-ylidene
1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (SIPr); 1,3-bis(2,6-
diisopropylphenyl)imidazol-2-ylidene (IPr); and 1,3-bis(2,4,6-tri-
methylphenyl)imidazol-2-ylidene (IMes).
(IPrCl);
(6) Ogoshi, S.; Hoshimoto, Y.; Ohashi, M. Chem. Commun. 2010,
46, 3354–3356.
(7) For details, see the Supporting Information.
4671
dx.doi.org/10.1021/ja109908x |J. Am. Chem. Soc. 2011, 133, 4668–4671