Iridium Diamine Catalyst for the Asymmetric Transfer Hydrogenation of Ketones

Vázquez-Villa, Henar; Reber, Stefan O.; Ariger, Martin A.; Carreira, Erick M.

doi:10.1002/anie.201102732

Cited by 82 publications

(31 citation statements)

References 42 publications

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“…Oil. R f =0.3 (EtOAc); [ α ]

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=−38.04 ( c =0.4 ethanol) lit . =−39.0 ( c =0.93 ethanol); 1 H NMR (300 MHz, CDCl 3 ): δ =8.46–8.33 (m, 2 H), 7.75–7.70 (m, 1 H), 7.24 (dd, J =8.0, 5.0 Hz, 1 H), 4.90 (q, J =6.5 Hz, 1 H), 4.5 (br s, 1 H, OH), 1.49 ppm (d, J =6.5 Hz, 3 H); 13 C NMR (75 MHz, CDCl3): δ =148.0, 147.0, 141.8, 133.5, 123.5, 67.5 25.1 ppm; elemental analysis calcd (%) for C 7 H 9 ON (123.07): C 68.27, H 7.37, N 11.37; found: C 68.55, H 7.67, N 11.10.…”

Section: Methodssupporting

confidence: 90%

Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts

et al. 2016

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The large consumption of freshwater in fermentations and bio‐transformations is a matter of concern for the sustainability of many bio‐processes. The use of seawater to perform bio‐processes is a sustainable alternative. In this work, we used marine yeasts from deep‐sub‐seafloor sediments grown in seawater as bio‐catalysts to perform the stereoselective reduction of different ketones, and the bio‐transformations were accomplished in seawater as well. Strains of Meyerozyma guilliermondii and Rhodotorula mucilaginosa were able to reduce different aromatic ketones with high molar conversions and moderate‐to‐high enantioselectivity with no significant differences between bio‐catalysis performed in seawater and freshwater. Finally, the selected marine yeasts were used for the reduction of key intermediates in seawater for the synthesis of molecules of pharmaceutical interest (desogestrel, norgestrel, gestodene, pramipexole).

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“…Oil. R f =0.3 (EtOAc); [ α ]

\frac{0pt}{25}

Section: Methodssupporting

confidence: 90%

Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts

et al. 2016

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“…Different approaches using either asymmetric transfer hydrogenation for the reduction of benzoylacetonitrile 5 with iridium(III) 22 and/or ruthenium(II) diamines complexes 23 or whole-cell catalysts 24,25 were studied. Recently our group displayed the reduction of the substrate 5 and its corresponding ethylated derivative 5b using Carreira's [Cp*Ir(diamine)(H 2 O)]SO 4 complexes in which the diamine ligand CAMPY and its derivatives were used as a source of chirality 26 with good stereoselectivity.…”

Section: Resultsmentioning

confidence: 99%

Simple 1,3-diamines and their application as ligands in ruthenium(ii) catalysts for asymmetric transfer hydrogenation of aryl ketones

et al. 2015

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In this research work simple unsymmetrical 1,3-diamines were studied. The synthesis of the diamines started from non-commercial available compounds. S-5a and S,S-5c were obtained by biocatalysis with non conventional yeast, Rhodotorula rubra MIM 147, with excellent 99% e.e. and d.e. up to 90%. Different approaches of synthesis were applied to the same backbone to study both the steric and electronic effects of the ligands. The reactivity of the corresponding ruthenium complexes was evaluated in the asymmetric hydrogen transfer reduction of acetophenone as a standard substrate and of other different aryl ketones, highlighting the flexibility of the six membered chelating ring. A screening of the reaction conditions indicated aqueous media in the presence of HCOONa as a hydrogen donor to be the best system for overcoming the lack of stereocontrol thus allowing us to obtain 56% e.e. in the reduction of acetophenone with the complex in which the ligand was diamine 1, revealed as the best in terms of reactivity and stereoselectivity also in the reduction of the other different aryl ketones, in particular for a-tetralone, i (63% e.e.).

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“…As the conversion of nitroketone 4 , which was obtained as major product from the large‐scale experiments, to nitroalcohol 2 is well established,40a,b, 47a we finally focused on the reduction of the nitrohydroxylation products 2 , 3 , and 5 to amino alcohols. Besides the above‐mentioned importance of such compounds in the field of pharmaceutical chemistry, such reactions could transform nitroalcohol 2 and its corresponding nitro nitrate 3 to the same amino alcohol, so that all nitrohydroxylation products 2–4 from the wet scrubber would be converted into only one compound.…”

Section: Resultsmentioning

confidence: 99%

Oxidative Nitration of Styrenes for the Recycling of Low‐Concentrated Nitrogen Dioxide in Air

2015

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The oxidative nitration of styrenes in ethyl acetate represents a metal-free, environmentally friendly, and sustainable technique to recover even low concentrations of NO2 in air. Favorable features are that the product mixture comprising nitroalcohols, nitroketones, and nitro nitrates simplifies at lower concentrations of NO2 . Experiments in a miniplant-type 10 L wet scrubber demonstrated that the recycling technique is well applicable on larger scales at which initial NO2 concentrations of >10 000 ppm were reliably reduced to less than 40 ppm.

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Iridium Diamine Catalyst for the Asymmetric Transfer Hydrogenation of Ketones

Cited by 82 publications

References 42 publications

Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts

Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts

Simple 1,3-diamines and their application as ligands in ruthenium(ii) catalysts for asymmetric transfer hydrogenation of aryl ketones

Oxidative Nitration of Styrenes for the Recycling of Low‐Concentrated Nitrogen Dioxide in Air

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