Cooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline

Le Wang, Cheng-Long Wang, Zi-Hao Li, Peng-Fei Lian, Jun-Chen Kang, Jia Zhou, Yu Hao, Ru-Xin Liu, He-Yuan Bai and Shu-Yu Zhang ()
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Le Wang: Shanghai Jiao Tong University
Cheng-Long Wang: Shanghai Jiao Tong University
Zi-Hao Li: Shanghai Jiao Tong University
Peng-Fei Lian: Shanghai Jiao Tong University
Jun-Chen Kang: Shanghai Jiao Tong University
Jia Zhou: Shanghai Jiao Tong University
Yu Hao: Shanghai Jiao Tong University
Ru-Xin Liu: Shanghai Jiao Tong University
He-Yuan Bai: Shanghai Jiao Tong University
Shu-Yu Zhang: Shanghai Jiao Tong University

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract Aliphatic allylic amines are common in natural products and pharmaceuticals. The oxidative intermolecular amination of C(sp3)-H bonds represents one of the most straightforward strategies to construct these motifs. However, the utilization of widely internal alkenes with amines in this transformation remains a synthetic challenge due to the inefficient coordination of metals to internal alkenes and excessive coordination with aliphatic and aromatic amines, resulting in decreasing the reactivity of the catalyst. Here, we present a regioselective Cu-catalyzed oxidative allylic C(sp3)-H amination of internal olefins with azodiformates to these problems. A removable bidentate directing group is used to control the regiochemistry and stabilize the π-allyl-metal intermediate. Noteworthy is the dual role of azodiformates as both a nitrogen source and an electrophilic oxidant for the allylic C-H activation. This protocol features simple conditions, remarkable scope and functional group tolerance as evidenced by >40 examples and exhibits high regioselectivity and excellent E/Z selectivity.

Date: 2024
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DOI: 10.1038/s41467-024-45875-y

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