Catalytic, high-speed tishchenko reaction using (2,7-dimethyl-1,8-biphenylenedioxy)bis(diisopropoxyaluminum) as a powerful bidentate catalyst

Homoleptic Lanthanide Amides as Homogeneous Catalysts for Alkyne Hydroamination and the Tishchenko Reaction

“…Even the recently reported highspeed Tishchenko catalyst, (2,7-dimethyl-1,8-biphenylenedioxy)bis(diisopropoxyaluminum) (entry 9) and (2,7-dimethyl-1,8-biphenylenedioxy)bis(dibenzoyloxyaluminum) (entry 10), do not reach the activity of 1 b. [40] Although we do not know of a more active catalyst for the Tishchenko reaction, two compounds are described in the literature ([(C 5 Me 5 ) 2 LaCH-(SiMe 3 ) 2 ] (entry 4), [32] and [Al(OCH 2 Ph) 3 ]) that could compete with 1 b. [(C 5 Me 5 ) 2 LaCH(SiMe 3 ) 2 ] would probably form [a] Reaction conditions (this work): 1 mol % catalyst in C 6 D 6 .…”

Lanthanide Formamidinates as Improved Catalysts for the Tishchenko Reaction

“…In addition, the recently introduced alkaline earth metal amides, such as [Ca{N(SiMe 3 ) 2 } 2 (thf) 2 ] (6) ( Table 1, Entry 9), cannot compete with the lanthanum catalysts. The use of the standard aluminum catalyst Al(OiPr) 3 [21,22] under the reaction conditions described above led to a low yield of product ( [33] or other aluminum-based catalysts (Table 1, Entry 13) [34] did not reach the level of activity of the lanthanum compounds. All classical transition-metal catalysts, [23][24][25] as well as boric acid [22] ( Table 1, Entries 14-18), failed to catalyze the reaction to complete conversion.…”

Borrowing Hydrogen in the Activation of Alcohols

“…[94] The bidentate aluminium complex 131 (Scheme 46) is a particularly efficient room temperature catalyst for the Tishchenko reaction. [95] The high reactivity is attributed to the double activation of the aldehyde by the two Lewis acid groups, although some other aluminium complexes which do not appear to act as bidentate catalysts can also give rapid reaction. [96] The iridium catalyst 132 is also an efficient room temperature catalyst for the Tishchenko reaction.…”