Hydrogen-Borrowing and Interrupted-Hydrogen-Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium

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Hydrogen-Borrowing and Interrupted-Hydrogen-Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium**

Reported herein is the use of catalytic [{Ir(cod)Cl}2 ] to facilitate hydrogen-borrowing reactions of ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pro-nucleophiles to the reaction mixture allowed a o...

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The amination of alcohols is an important transformation in chemistry. The redox-neutral (i.e., hydrogen-borrowing) asymmetric amination of alcohols is enabled by the combination of an alcohol dehydrogenase (ADH) with an amine dehydrogenase (AmDH). In this work, we enhanced the efficiency of hydrogen-borrowing biocatalytic amination by co-immobilizing both dehydrogenases on controlled porosity ...

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Iridium-catalyzed selective α-methylation of ketones with methanol.

Iridium-catalyzed selective α-dimethylation and α-methylation of ketones or phenylacetonitriles, using methanol as the methylating agent, were achieved. In addition, three-component cross α-methyl-alkylation was successfully performed using methyl ketones with methanol and primary alcohols with long-chain alkyl groups. This method provides a very convenient direct route to α-methylated ketones,...

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A ruthenium(ii) bis(phosphinophosphinine) complex as a precatalyst for transfer-hydrogenation and hydrogen-borrowing reactions.

The 2-phosphinophosphinine 2-PPh2-3-Me-6-SiMe3-PC5H2 (2) has been prepared and was shown to act as a κ2-chelating ligand in cis-[RuCl2(2)2] (4). Complex 4 was a competent precatalyst for the room temperature transfer hydrogenation of acetophenone (0.1 mol% 4 and 0.5 mol% KOtBu) and the conversion of methanol/ethanol mixtures to the advanced biofuel isobutanol in 50% yield and 96% selectivity.

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ژورنال

عنوان ژورنال: Angewandte Chemie International Edition

سال: 2014

ISSN: 1433-7851

DOI: 10.1002/anie.201410391