Asymmetric α-C(sp3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis

Jianyu Li, Sheng Gong, Shaolun Gao, Jianfeng Chen (), Wen-Wen Chen and Baoguo Zhao ()
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Jianyu Li: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University
Sheng Gong: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University
Shaolun Gao: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University
Jianfeng Chen: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University
Wen-Wen Chen: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University
Baoguo Zhao: Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University

Nature Communications, 2024, vol. 15, issue 1, 1-8

Abstract: Abstract Primary alkyl amines are highly reactive in N-nucleophilic reactions with electrophiles. However, their α-C−H bonds are unreactive towards electrophiles due to their extremely low acidity (pKa ~57). Nonetheless, 1,8-diazafluoren-9-one (DFO) can activate primary alkyl amines by increasing the acidity of the α-amino C−H bonds by up to 1044 times. This makes the α-amino C−H bonds acidic enough to be deprotonated under mild conditions. By combining DFO with an iridium catalyst, direct asymmetric α-C−H alkylation of NH2-unprotected primary alkyl amines with allylic carbonates has been achieved. This reaction produces a wide range of chiral homoallylic amines with high enantiopurities. The approach has successfully switched the reactivity between primary alkyl amines and allylic carbonates from intrinsic allylic amination to the α-C−H alkylation, enabling the construction of pharmaceutically significant chiral homoallylic amines from readily available primary alkyl amines in a single step.

Date: 2024
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DOI: 10.1038/s41467-024-45131-3

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