Transition‐Metal Free Electrophilic Aminations of PolyfunctionalO‐2,4,6‐Trimethylbenzoyl Hydroxylamines with Zinc and Magnesium Organometallics

Sunagatullina, Alisa S.; Hess, Andreas; Kremsmair, Alexander; Li, Yifan; Chen, Yi‐Hung und Knochel, Paul (2023): Transition‐Metal Free Electrophilic Aminations of PolyfunctionalO‐2,4,6‐Trimethylbenzoyl Hydroxylamines with Zinc and Magnesium Organometallics. In: Angewandte Chemie International Edition, Bd. 62, Nr. 30

Abstract

We reported a new electrophilic amination of various primary, secondary and tertiary alkyl, benzylic, allylic zinc and magnesium organometallics with O-2,4,6-trimethylbenzoyl hydroxylamines (O-TBHAs) in 52–99 % yield. These O-TBHAs displayed an excellent long-term stability and were readily prepared from various highly functionalized secondary amines via a convenient 3 step procedure. The amination reactions showed remarkable chemoselectivity proceeding without any transition-metal catalyst and were usually complete after 1–3 h reaction time at 25 °C. Furthermore, this electrophilic amination also provided access to enantioenriched tertiary amines (up to 88 % ee) by using optically enriched secondary alkylmagnesium reagents of the type s-AlkylMgCH2SiMe3.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1433-7851
• Sprache: Englisch