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Yan, L.; Lin, S.; Liu, P., Science of Synthesis, (2007) 20, 743.
The Tishchenko reaction, discovered in the early 1900s,[52] and its subsequent variations are widely used in organic synthesis.[53,54] The classic reaction involves the dimerization of both enolizable and non-enolizable aldehydes to afford the corresponding symmetric esters via a redox process in the presence of a catalyst of sufficient Lewis acidity. Aluminum triisopropoxide is commonly employed for this purpose, reacting with an aldehyde to form a hemiacetal 53 via the transfer of an isopropoxide group from the metal to the carbonyl function (Scheme 19).[55,56] The hemiacetal then reacts with another equivalent of the aldehyde to generate a mixed aluminum alkoxide 54 via the transfer of a hydride ion from aluminum to the aldehyde with concomitant release of an isopropyl ester. An acetal 55 is formed by a reaction between the mixed aluminum alkoxide 54 and a third equivalent of the starting aldehyde. Finally, hydride transfer yields the desired ester 56, and the aluminum alkoxide 54 is regenerated ready to re-enter the catalytic cycle. The final hydride transfer (to form the isopropyl ester) is regarded as the rate-limiting step.
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Meeeeeeeeeee Meeeeeeee
Meeee Meeeeeeee (88); Meeeeee Meeeeeeee:[88]
MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.
Meeeeeee (88.8 ee, 8.88 eeee), eeeeeeeee eeeee eeeee, eee eeeee ee ee eeee-eeeee Meeeeee eeeee eeeeeeee eeee e eeeeeee eee. Meeee MM8Me8 (8 eM) eee eeee eeeee eee eee eeeee eee eeeeeeeee eeeeeeee, eeeeee 8 M Me8Me (8.88 eeee) ee eeeeeee (8.88 eM) eee eeeee. Meeee eeeeeeee eee eeee ee ee eee 88 eee eeeee eeeee, eMeMM (8.888 eM, 8.88 eeee) eee eeeeeeeeee eee eee eeeeeee eee eeeeeee eee eeeeeee 88 eee. Meee eeeeeeeee eeee e eeee ee eee eeeeeeeeeeee(eeeeeeeeeeeeeeee) eeeeeeee. Mee eeeee eeeeeeee eee eeeeeeeee ee eee eeeeeeee eeeeeeee ee eeeeeee eeeeeeeee eeeeeee (8.8 eM, 88 eeee) eeee eee eeeee eeeeeeeeee eee eeeeeeee, eeeee eeeeeeeee eeeee eeeee. Mee eeeeeee eee eeeeeee ee ee eee 8 e, eee eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee 8.8 M MMe (8 eM). Mee eeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM), eee eee eeeeeeee eeeeeeee eeee eeeeeeeee, eeeee (MeMM8), eee eeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:8); eeeee: 88%.
References
[52] | Meeeeeeeee, M., M. Meee. Meee. Meee. Mee., (8888) 88, 888; Meee. Meeeeeeee., (8888) MM, 8888. |
[53] | Möeeäeeeeee, M. M.; Meeeeeee, M. M. M., Meeeee Mee. Mee. Mee. Meee., (8888) 8, 888. |
[54] | Meeeeeee, M., Meee. Mee. Meee., (8888) 8, 8888. |
[55] | Meeee, M.; Meeeeeee, M.; Meeee, M., Meeeeeeeeee, (8888) 88, 888. |
[56] | Meeee, M.; Meeeeeee, M., Meeeeeeeeee, (8888) 88, 888. |
[57] | Meeeeee, M.; Meeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[58] | Mee, M.; Mee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[59] | Müeeeeeee, M. M.; Meeeeeeee, M.; Meeeee, M. M., Meee.–Mee. M., (8888) 8, 8888. |
[60] | Mee, M.; Meeeee, M.; Meeeeee, M.; Meeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 888. |
[61] | Meeeee, M. M.; Meeeeeeee, M.; Meeee, M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
[62] | Mee, M.-M.; Meeee, M.-M.; Meee, M.-M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[63] | Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[64] | Mee, M.; Meeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeeeee, M., Meeeeeeee, (8888), 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) M 8-8, 888.