- Sustainable Alkylation of Nitriles with Alcohols by Manganese Catalysis
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A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This alkylation reaction uses naturally abundant alcohols and readily available nitriles as coupling partners. The reaction tolerates a wide range of functional groups and heterocyclic moieties, efficiently providing useful cyanoalkylated products with water as the only side product. Importantly, methanol can be used as a C1 source and the chemoselective C-methylation of nitriles is achieved. The mechanistic investigations support the multiple role of the metal-ligand manganese catalyst, the dehydrogenative activation of the alcohol, α-C-H activation of the nitrile, and hydrogenation of the in-situ-formed unsaturated intermediate.
- Borghs, Jannik C.,Tran, Mai Anh,Sklyaruk, Jan,Rueping, Magnus,El-Sepelgy, Osama
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p. 7927 - 7935
(2019/06/24)
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- Efficient solvent-free selective monoalkylation of arylacetonitriles with mono-, bis-, and tris-primary alcohols catalyzed by a Cp*Ir complex
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Our objectives were to develop catalytic atom-economic processes accessing and/or incorporating versatile functionality using aryl/heteroaryl acetonitriles as substrates. We report essentially solvent-free [Cp*IrCl 2]2 catalyzed redox neutral processes whereby substituted acetonitriles react with primary alcohols to deliver monosubstituted aryl/heteroaryl acetonitriles in excellent yield. We further demonstrate that such processes can be achieved by conventional or microwave heating and that bis- and tris-primary alcohols are also processed efficiently.
- Loefberg, Christian,Grigg, Ronald,Whittaker, Mark A.,Keep, Ann,Derrick, Andrew
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p. 8023 - 8027
(2007/10/03)
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