A Modified System for the Synthesis of Enantioenriched N‐Arylamines through Copper‐Catalyzed Hydroamination. (12th June 2018)

• Record Type: Journal Article
• Authors: Ichikawa, Saki; Zhu, Shaolin; Buchwald, Stephen L.
• Is Part Of: Angewandte Chemie. Volume 130:Number 28(2018)
• Page Start: 8850
• Page End: 8854
• Publication Date: 2018-06-12
• Subjects: Asymmetrische Synthesen -- Homogene Katalyse -- Hydroaminierungen -- Kupfer -- N-Arylamine; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201803026
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Despite significant recent progress in copper‐catalyzed enantioselective hydroamination chemistry, the synthesis of chiral N ‐arylamines, which are frequently found in natural products and pharmaceuticals, has not been realized. Initial experiments with N ‐arylhydroxylamine ester electrophiles were unsuccessful and, instead, their reduction in the presence of copper hydride (CuH) catalysts was observed. Herein, we report key modifications to our previously reported hydroamination methods that lead to broadly applicable conditions for the enantioselective net addition of secondary anilines across the double bond of styrenes, 1, 1‐disubstituted olefins, and terminal alkenes. NMR studies suggest that suppression of the undesired reduction pathway is the basis for the dramatic improvements in yield under the reported method. Abstract : Ein effizientes Syntheseverfahren für enantiomerenangereicherte N ‐Arylamine baut auf einer bekannten Hydroaminierung auf und nutzt einen Kupfer(I)‐hydrid(CuH)‐Katalysator, um vielfältige Olefine und N ‐Arylhydroxylamine unter optimierten Bedingungen miteinander umzusetzen. Der Erfolg der Methode beruht auf dem Zusatz von t BuOH und PPh3 zum Reaktionsgemisch.