Transition-Metal Free Electrophilic Aminations of Polyfunctional O-2,4,6-Trimethylbenzoyl Hydroxylamines with Zinc and Magnesium Organometallics |
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| Authors: | Dr. Alisa S. Sunagatullina Dr. Andreas Hess Dr. Alexander Kremsmair Yifan Li Yi-Hung Chen Prof. Dr. Paul Knochel |
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| Affiliation: | 1. Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany;2. The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, 430072 Wuhan, Hubei, P. R. China |
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| 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. |
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| Keywords: | Amines Asymmetric Synthesis Electrophilic Amination Organomagnesium Reagents Organozinc Reagents |
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