Phosphine-Catalyzed Z-Selective Carbofluorination of Alkynoates Bearing an N-Heteroarene Unit

Hayato Fujimoto; Shisato Yamamura; Namiki Takenaka; Mamoru Tobisu

doi:10.1055/a-1948-3234

Synthesis, Table of Contents

Synthesis 2023; 55(06): 899-906
DOI: 10.1055/a-1948-3234

special topic

Synthetic Advancements Enabled by Phosphorus Redox Chemistry

Phosphine-Catalyzed Z-Selective Carbofluorination of Alkynoates Bearing an N-Heteroarene Unit

Hayato Fujimoto

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

,

Shisato Yamamura

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

,

Namiki Takenaka

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

,

Mamoru Tobisu ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

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Abstract

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Abstract

We report herein on the phosphine-catalyzed Z-selective carbofluorination of alkynoates bearing an N-heteroarene unit, by using acyl fluorides as bifunctional reagents. This reaction proceeds through a pentacoordinate fluorophosphorane(V) intermediate, resulting in the formation of a C–F bond by a ligand coupling process. The Z-selectivity is attributed to the thermodynamic stabilization of a Z-isomer by orbital interactions between lone pair electrons of an N-heteroarene and the π* orbital of a carbonyl group.

Key words

phosphine redox catalysis - fluorophosphorane - carbofluorination - monofluoroalkene - n→π* interaction

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References

References

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