Rhodium Phosphine–Phosphite Catalysts in the Hydrogenation of Challenging <i>N</i>-(3,4-dihydronaphthalen-2-yl) Amide Derivatives

Arribas, Inmaculada; Rubio, M.; Kleman, Patryk; Pizzano, Antonio

doi:10.1021/jo400345v

Cited by 38 publications

(16 citation statements)

References 71 publications

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“…High efficiency and enantioselectivity have usually been achieved by utilizing such phosphine–phosphite ligands with more than one chiral element 4a. However, for enamide substrates, rather few phosphine–phosphite/metal catalysts have been found to be highly enantioselective in the asymmetric hydrogenation 5a,5b,5g,6c. Considering the widespread application of phosphine–phosphite ligands4a and as a continuation of our ongoing endeavor to develop effective chiral supramolecular catalysts based on crown ethers,2g,6h,6i herein, we report the preparation of a new class of metallacrown ether catalysts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Elusive Chloropnictenium Ions

Hering‐Junghans

Thomas

Villinger

et al. 2015

Chemistry A European J

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This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [(R)Ar*N(SiMe)ECl][A] ((R)Ar* = 2,6-(CHPh2)-4-R-C6H2, R = Me, tBu; E = Sb, Bi; A(-) = GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the (R)Ar* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4-dimethylaminopyridine (dmap) was investigated.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Elusive Chloropnictenium Ions

Hering‐Junghans

Thomas

Villinger

et al. 2015

Chemistry A European J

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“…Most remarkably, a Rh catalyst based on ligand L22 , provided an outstanding enantioselectivity of 94% ee in the hydrogenation of N ‐(3,4‐dihydro‐2‐naphthalenyl)acetamide 62. Inspired by this result, Pizzano and co‐workers applied conventional P‐OP ligands in this reaction 63. Following extensive screening, ligand L8d , characterized by a P‐stereogenic phosphine fragment, provided the highest enantioselectivities, with values ranging from 83 to 93% ee in the hydrogenation of several enamides of this type (Scheme ).…”

Section: Recent Applications Of P‐op Ligands In Asymmetric Catalysismentioning

confidence: 98%

Features and Application in Asymmetric Catalysis of Chiral Phosphine–Phosphite Ligands

Pizzano

2016

The Chemical Record

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Chiral phosphine-phosphites are a class of ligands for asymmetric catalysis characterized by two coordinating functionalities with different electronic properties. These ligands also possess a highly modular structure and, due to versatile synthetic processes, they can be tuned precisely in the catalyst optimization process. Research regarding the application of these ligands in several enantioselective catalytic processes has provided outstanding results in a good number of them. These processes include not only Rh catalyzed reactions, such as olefin hydrogenation and hydroformylation, but also other reactions, such as hydrogenation of olefins and imines by Ru complexes, of imines and N-heterocycles by Ir derivatives, allyl alkylation or conjugate addition by Cu catalysts, or hydrocyanation of olefins by Ni ones. Overall, the use of these ligands has led to the preparation of a wide variety of chiral building blocks with high enantiomeric excess. Therefore, phosphine-phosphites have become in an important class of ligands in asymmetric catalysis.

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“…Most of the catalysts, predominantly based on Rh and Ru, provide unsatisfactory enantioselectivities in the asymmetric hydrogenation of cyclic β‐enamides . Among the most successful examples (Figure ),,,,,, Ratovelomanana et al. reported the synthesis 3‐aminochromanes with enantioselectivities of up to 96 % ee by using Ru–diphosphine catalysts .…”

Section: Introductionmentioning

confidence: 99%

Phosphite‐Thiother Ligands Derived from Carbohydrates allow the Enantioswitchable Hydrogenation of Cyclic β‐Enamides by using either Rh or Ir Catalysts

Margalef

Pàmies

Diéguez

2016

Chemistry A European J

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Phosphite-thioether ligands with a simple modular architecture, derived from inexpensive l-(+)-tartaric acid and d-mannitol, have been for the first time successfully applied (ee values up to 99 %) in the synthesis of 2-aminotetralines and 3-aminochromanes by metal-catalyzed asymmetric hydrogenation of cyclic β-enamides. The ligands have the advantages of the robustness of the thioether/phosphite moieties and the extra control provided by the flexibility of the chiral pocket through the presence of a biaryl phosphite group and a modular carbohydrate-derived backbone. Moreover, they are solid and stable to air and they are therefore easy to handle, manipulate, and store. Usefully, both enantiomers of the hydrogenated products were obtained by simply switching from Rh to Ir. Low hydrogen pressure and environmentally friendly propylene carbonate can be used, with no loss of selectivity.

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Rhodium Phosphine–Phosphite Catalysts in the Hydrogenation of Challenging N-(3,4-dihydronaphthalen-2-yl) Amide Derivatives

Cited by 38 publications

References 71 publications

Synthesis of Elusive Chloropnictenium Ions

Synthesis of Elusive Chloropnictenium Ions

Features and Application in Asymmetric Catalysis of Chiral Phosphine–Phosphite Ligands

Phosphite‐Thiother Ligands Derived from Carbohydrates allow the Enantioswitchable Hydrogenation of Cyclic β‐Enamides by using either Rh or Ir Catalysts

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