Cooperative Effects between Chiral Cpx–Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C−H Amidations of Phosphine Oxides

An enantioselective C−H amidation of phosphine oxides by using an iridium(III) catalyst bearing an atropchiral cyclopentadienyl (Cpx) ligand is reported. A very strong cooperative effect between the chiral Cpx ligand and a phthaloyl tert‐leucine enabled the transformation. Matched–mismatched cases o...

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Bibliographic Details
Published in:Angewandte Chemie 2017-11, Vol.129 (47), p.15284-15288
Main Authors: Jang, Yun‐Suk, Dieckmann, Michael, Cramer, Nicolai
Format: Article
Language:eng ; ger
Subjects:
Asymmetrische Katalyse
C-H-Aktivierung
Carboxylic acids
Catalysis
Catalysts
Chemistry
Chiraler Cp-Ligand
Enantiomers
Iridium
Leucine
Ligands
Oxides
P-Chiralität
Phosphine
Phosphine oxide
Phosphorus
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Summary:An enantioselective C−H amidation of phosphine oxides by using an iridium(III) catalyst bearing an atropchiral cyclopentadienyl (Cpx) ligand is reported. A very strong cooperative effect between the chiral Cpx ligand and a phthaloyl tert‐leucine enabled the transformation. Matched–mismatched cases of the different acid enantiomers are shown. The amidated P‐chiral arylphosphine oxides are formed in yields of up to 95 % and with excellent enantioselectivities of up to 99:1 er. Enantiospecific reduction provides access to valuable P‐chiral phosphorus(III) compounds. Katalytischer Handschlag: Ein kooperativer Effekt zwischen einem chiralen CpxIrIII‐Komplex und einer chiralen Carbonsäure ermöglicht hoch enantioselektive C‐H‐Amidierungen von Phosphinoxiden mit bis zu 99:1 er. Matched‐Mismatched‐Paare haben einen starken Einfluss auf die Reaktivität und Selektivität.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201708440