Sunagatullina Alisa S, Hess Andreas, Kremsmair Alexander, Li Yifan, Chen Yi-Hung, Knochel Paul
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.
The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, Hubei, P. R. China.
Angew Chem Int Ed Engl. 2023 Jul 24;62(30):e202304445. doi: 10.1002/anie.202304445. Epub 2023 Jun 19.
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-AlkylMgCH SiMe .
我们报道了一种新型的亲电胺化反应，该反应利用O-2,4,6-三甲基苯甲酰基羟胺（O-TBHA）与各种伯、仲、叔烷基、苄基、烯丙基锌和镁有机金属化合物进行反应，产率为52-99%。这些O-TBHA具有出色的长期稳定性，并且可以通过简便的三步法由各种高度官能化的仲胺轻松制备。胺化反应显示出显著的化学选择性，无需任何过渡金属催化剂即可进行，通常在25℃下反应1-3小时后即可完成。此外，通过使用s-烷基MgCH SiMe类型的光学富集仲烷基镁试剂，这种亲电胺化反应还能够制备对映体富集的叔胺（ee值高达88%）。
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