Tishchenko反应

Tishchenko反应，两分子的醛通过歧化反应制备酯的反应。

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反应机理

烷氧基铝作为 Lewis酸和一分子醛络合，络合得到的活化的羰基更容易被第二分子的醛进行加成，生成半缩醛中间体：

生成的半缩醛中间体通过分子内的1,3-氢迁移得到铝配位的酯。

此反应可能的副反应是催化剂的烷氧基参与下述历程：

可以通过降低反应温度和减少催化剂的量来减少此副反应的影响。

最新文献

Nickel-Catalyzed Selective Conversion of Two Different Aldehydes to Cross-Coupled Esters
Y. Hoshimoto, M. Ohashi, S. Ogoshi, J. Am. Chem. Soc., 2011, 133, 4668-4671.

The Thiolate-Catalyzed Intermolecular Crossed Tishchenko Reaction: Highly Chemoselective Coupling of Two Different Aromatic Aldehydes
S. P. Curran, S. J. Connon, Angew. Chem. Int. Ed., 2012, 51, 10866-10870.

Lithium Bromide as a Flexible, Mild, and Recyclable Reagent for Solvent-Free Cannizzaro, Tishchenko, and Meerwein-Ponndorf-Verley Reactions
M. M. Mojtahedi, E. Akbarzadeh, R. Sharifi, M. S. Abaee, Org. Lett., 2007, 9, 2791-2793.

Catalytic Meerwein-Ponndorf-Verley (MPV) and Oppenauer (OPP) Reactions: Remarkable Acceleration of the Hydride Transfer by Powerful Bidentate Aluminum Alkoxides
T. Ooi, T. Miura, Y. Itagaki, H. Ichikawa, K. Maruoka, Synthesis, 2002, 279-291.

Selenide Ions as Catalysts for Homo- and Crossed-Tishchenko Reactions of Expanded Scope
S. P. Curran, S. J. Connon, Org. Lett., 2012, 14, 1074-1077.

Nucleophile- or Light-Induced Synthesis of 3-Substituted Phthalides from 2-Formylarylketones
D. C. Gerbino, D. Augner, N. Slavoy, H.-G. Schmalz, Org. Lett., 2012, 14, 2338-2341.

Direct Catalytic Asymmetric Aldol-Tishchenko Reaction
V. Gnanadesikan, Y. Horiuchi, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc., 2004, 126, 7782-7783.

编译自：Organic Chemistry Portal