CC BY ND NC 4.0 · Synlett 2019; 30(04): 503-507
DOI: 10.1055/s-0037-1611669
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Manganese Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using Chiral Oxamide Ligands

Jacob Schneekönig
,
,
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany   Email: Matthias.Beller@catalysis.de
› Author Affiliations
This work was supported by the state of Mecklenburg Vorpommern.
Further Information

Publication History

Received: 14 December 2018

Accepted after revision: 10 January 2018

Publication Date:
25 January 2019 (eFirst)

 

Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

The asymmetric transfer hydrogenation of ketones using isopropyl alcohol (IPA) as hydrogen donor in the presence of novel manganese catalysts is explored. The selective and active systems are easily generated in situ from [MnBr(CO)5] and inexpensive C 2-symmeric bisoxalamide ligands. Under the optimized reaction conditions, the Mn-derived catalyst gave higher enantioselectivity compared with the related ruthenium catalyst.

Supporting Information

 
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  • 17 General procedure for the ATH of prochiral ketones: Ligand L4a (6.6 mg, 0.02 mmol, 2 mol%) and MnBr(CO)5 (16.2 mg, 0.06 mmol, 6 mol%) were placed in a flame-dried 25 mL Schlenk tube equipped with a PTFE-coated stirring bar, followed by anhydrous degassed isopropyl alcohol (2 mL). The suspension was stirred for 10 min at room temperature. A solution of potassium tert-butoxide (22.4 mg, 0.2 mmol, 20 mol% in 2 mL iPrOH) was added and the resulting yellowish solution was stirred for a further 10 min at room temperature. A solution of the desired ketone (1 mmol in 2 mL iPrOH) was then added and the mixture was heated to 80 °C and kept at this temperature for 20 h. The reaction solution was allowed to cool to room temperature and filtered through a plug of silica and washed with iPrOH (3 × 5 mL). Hexadecane (20 mg) was added to the reaction solution. The yield of the desired alcohol was determined by GC analysis using hexadecane as internal standard, and the ee was determined either by GC or HPLC analysis using an appropriate separation method (see the Supporting Information for further information).