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. 2017 May 22;56(22):6228-6231.
doi: 10.1002/anie.201611186. Epub 2017 Jan 9.

Rethinking the Claisen-Tishchenko Reaction

Stacey A Morris  1 , Dmitry G Gusev  1
Affiliations

Rethinking the Claisen-Tishchenko Reaction

Stacey A Morris et al. Angew Chem Int Ed Engl. .

Abstract

Pincer-type complexes [OsH2 (CO){PyCH2 NHCH2 CH2 NHPtBu2 }] and [OsH2 (CO){HN(CH2 CH2 PiPr2 )2 }] catalyze the disproportionation reaction of aldehydes via an outer-sphere bifunctional mechanism achieving turnover frequencies up to 14 000 h-1 . The N-H group of the catalysts is a key player in this process, elucidated with the help of DFT calculations.

Keywords: aldehyde disproportionation; bifunctional catalysts; ester synthesis; metal-ligand cooperation; pincer complexes.

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