Tishchenko Reaction
Tishchenko Reaction
The Tishchenko Reaction Is A Disproportionation Reaction That Allows The Preparation Of Esters From Two Equivalents Of An Aldehyde.
Mechanism Of The Tishchenko Reaction
The Aluminium Alkoxide Acts As A Lewis Acid To Coordinate With One Molecule Of The Aldehyde, And To Facilitate The Addition Of A Second Equivalent Of Aldehyde, Generating A Hemiacetal Intermediate:
This Species Undergoes An Intramolecular 1,3-hydride Shift That Results In The Production Of The Aluminium-coordinated Ester.
A Potential Side Reaction Is The Involvement Of One Of The Alkoxide Groups From The Catalyst:
This Can Be Minimised, If The Reaction Is Conducted At Low Temperatures And Low Catalyst Loadings.
Recent Literature
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.