Recent Advances in C—H Fluorination and Amination with N-Fluorobenzenesulfonimide

doi:10.6023/cjoc202006069

Abstract

The nitrogen- and fluorine-containing molecules display multiple important bioactivities which are crucial compounds in medicinal chemistry. The strategy relies on the transition-metal-catalyzed C—H amination and fluorination has received much attention due to its atom- and step-economy, providing an alternative to the synthesis of many natural alkaloids and fluorides.N-Fluorobenzenesulfonimide (NFSI) consists of the fluoride atom and the nitrogen-containing functionality, it is frequently used in the reactions based on transition-metal-catalyzed C—H activation to construct both C—N and C—F bonds. In this mini-review, the recent research advances in the formation of C—N and C—F bonds through transition-metal-catalyzed C—H with NSFI are reviewed. The reaction scopes and mechanisms are discussed in details, and the limitations of current procedures and the prospects for the future are summarized.

Key words: N-fluorobenzenesulfonimide, fluorination, amination, C—H activation, transition-metal catalysis

Cite this article

Weilin Wang, Weidong Chen, Junfei Luo, Pan Xie. Recent Advances in C—H Fluorination and Amination with N-Fluorobenzenesulfonimide[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 543-552.

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Fig. & Tab. 8

Scheme 1. C—H activation with common coupling parther and C—H activation with NFSI

Scheme 2. Catalytic cycle for Pd-catalyzed C—H fluorination with NFSI

Scheme 3. Catalytic cycle for transient directing group-assisted Pd-catalyzed C—H fluorination

Scheme 4. Mechanism for Rh-catalyzed C—H amination

Scheme 5. Mechanism for Pd-catalyzed C(sp3)—H amination

Scheme 6. Catalytic cycle for bidentate directing group-assisted Pd-catalyzed β-C(sp 3)—H amination

Scheme 7. Catalytic cycle for Pd-catalyzed remote C(sp2)—H amination.

Scheme 8. Catalytic cycle for Pd-catalyzed remote C(sp3)—H amination

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N-氟代苯磺酰亚胺参与的过渡金属催化C—H氟化和胺化的研究进展