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Synlett 2005(9): 1450-1452  
DOI: 10.1055/s-2005-868493
LETTER
© Georg Thieme Verlag Stuttgart · New York

Tishchenko Reaction Using an Iridium-Ligand Bifunctional Catalyst

Takeyuki Suzuki*, Taichiro Yamada, Tomohito Matsuo, Kazuhiro Watanabe, Tadashi Katoh*
Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-Ku, Sendai, Miyagi 981-8558, Japan
Fax: +81(22)2752013; e-Mail: suzuki-t@tohoku-pharm.ac.jp; e-Mail: katoh@tohoku-pharm.ac.jp;
Further Information

Publication History

Received 8 March 2005
Publication Date:
25 April 2005 (online)

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Abstract

Tishchenko reaction of aldehydes in the presence of an amino alcohol-based Ir bifunctional catalyst was developed. The reaction proceeds with 1 mol% of the catalyst and 20-30 mol% of K2CO3 in acetonitrile at room temperature to give the corresponding dimeric esters in good yield.

Key words

aldehydes - esters - hydrogen transfer - iridium catalyst - Tishchenko reaction

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13

Although Cs2CO3 also showed similar reactivity (ca. 90%), the use of other bases, such as Na2CO3, KHCO3, KOAc, and Et3N resulted in lower reactivity (<10% yield). t-BuOK afforded the aldol condensation product without forming the dimeric ester.

14

Although TONs were not optimized at the moment, they were roughly calculated to be in range between 43 and 49 for most substrates.

16

In a control experiment, no reaction took place without Ir complex (in the presence of K2CO3).

17

In most cases, a small amount of alcohol remained even after the aldehyde was completely consumed.