Unsymmetrical hybrid chiral diphosphorus ligands bearing a spirocyclic phosphoramidite scaffold have been developed and successfully applied in the iridium-catalyzed asymmetric hydrogenation of imines. With this newly developed chiral iridium catalytic system, a wide range of imines including sterically hindered ones could be hydrogenated to give the corresponding optically active amines in high yields (up to >99%) and with excellent enantioselectivities (up to >99% ee). The utility of this hydrogenation has been demonstrated by the preparation of the chiral fungicide ()-benalaxyl.
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Tropos Diphenylmethane-Based Phosphine-Phosphoramidite Ligands: Design, Synthesis, and Application in Catalytic Asymmetric Hydrogenation.
Org Lett
January 2025
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
A series of chiral hybrid diphosphorus ligands incorporating a conformationally flexible tropos diphenylmethane-based phosphoramidite unit have been developed and evaluated in the Rh-catalyzed asymmetric hydrogenation of 2-(1-arylvinyl)anilides and α-enamides, leading to up to >99% yield and 99% enantiomeric excess. Preliminary results from comparative studies showcased the extraordinary catalytic performance of these chiral tropos phosphine-phosphoramidite ligands, with a competency essentially superior to those of well-established ligands with a regular rigid backbone.
View Article and Find Full Text PDFFormation of a Hexaphosphido Cobalt Complex through P-P Condensation.
Chemistry
October 2023
University of Regensburg, Institute of Inorganic Chemistry, 93040, Regensburg, Germany.
The reaction between diphosphorus derivatives [( Im )P (Dipp)]OTf (1[OTf]) and [( Im )P (Dipp)Cl] (1[Cl]) with the cyclotetraphosphido cobalt complex [K(18c-6)][(PHDI)Co(η -cyclo-P )] (2) leads to the formation of complex [(PHDI)Co{η -cyclo-P (Dipp)( Im )}] (3), which features an unusual hexaphosphido ligand [ Im =4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl, Dipp=2,6-diisopropylphenyl, 18c-6=18-crown-6, PHDI=bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine]. Complex 3 was obtained as a crystalline material with a moderate yield at low temperature. Upon exposure to ambient temperature, compound 3 slowly transforms into two other compounds, [K(18c-6)][(PHDI)Co(η -P Dipp)] (4) and [(PHDI)Co{cyclo-P ( Im )}] (5).
View Article and Find Full Text PDFDevelopment of spirocyclic phosphoramidite-based hybrid diphosphorus ligands for enantioselective iridium-catalyzed hydrogenation of imines.
Org Biomol Chem
November 2022
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
Unsymmetrical hybrid chiral diphosphorus ligands bearing a spirocyclic phosphoramidite scaffold have been developed and successfully applied in the iridium-catalyzed asymmetric hydrogenation of imines. With this newly developed chiral iridium catalytic system, a wide range of imines including sterically hindered ones could be hydrogenated to give the corresponding optically active amines in high yields (up to >99%) and with excellent enantioselectivities (up to >99% ee). The utility of this hydrogenation has been demonstrated by the preparation of the chiral fungicide ()-benalaxyl.
View Article and Find Full Text PDFLeveraging Metal and Ligand Reactive Sites for One Pot Reactions: Ligand-Centered Borenium Ions for Tandem Catalysis with Palladium.
Chemistry
November 2022
Department of Chemistry, The University of Iowa, Iowa City, Iowa, 52242, USA.
Tandem catalysts that perform two different organic transformations in a single pot are highly desirable because they enable rapid and efficient assembly of simple organic building blocks into more complex molecules. Many examples of tandem catalysis rely on metal-catalyzed reactions involving one or more metal complexes. Remarkably, despite surging interest in the development of chemically reactive (i.
View Article and Find Full Text PDFThe generation of diphosphorus molecules P under mild conditions in solution is a useful strategy to generate diphosphines [4+2] cycloadditions. We recently described the release of P units from the nickel butterfly complex [{(IMes)Ni(CO)}(μ,η:η-P)] (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes.
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