Recent Advances in the Catalytic Transformations to Access Alkylsulfonyl Fluorides as SuFEx Click Hubs

Product Manager：Nick Wilde

ABSTRACT

The quest for innovative and effective techniques to produce sulfonyl fluorides is of significant interest due to their extensive applications across various fields. Sulfur(VI) fluoride exchange (SuFEx) click chemistry has recently gained prominence as one of the leading methods in this domain. Consequently, the development of efficient catalytic methodologies for synthesizing alkylsulfonyl fluorides has become a focal point in organic chemistry. While there has been substantial progress in the synthesis of arylsulfonyl fluorides, methods for generating aliphatic sulfonyl fluorides have not been as thoroughly investigated. This review highlights recent advancements in four distinct strategies for producing alkylsulfonyl fluorides: (i) photoredox catalysis, (ii) electrocatalysis, (iii) transition-metal catalysis, and (iv) organocatalysis. These methods yield various sulfonyl fluorides that serve as bioactive compounds and building blocks for subsequent SuFEx transformations.

INTRODUCTION

Sulfonyl fluorides are vital building blocks in chemical synthesis, finding wide-ranging applications in materials science, chemical biology, and drug discovery. 1-3 Since 2014, Sharpless and his team have illustrated that the sulfur(VI) fluoride exchange(SuFEx)  reaction is a promising new click chemistry approach, characterized by the unique reactivity and stability of organosulfur fluorides.4-6 The Huisgen azide-alkyne cycloaddition, recognized as the first-generation click reaction, is highly valued for its ability to ligate azides and alkynes under the influence of mild copper catalysis.7-10 Click reactions are advantageous due to their compatibility with aqueous and oxygen-tolerant environments, leading to high product yields. Compared to sulfonyl chlorides, sulfonyl fluorides exhibit greater stability under both acidic and basic conditions.11

Sulfur(VI)-containing compounds are extensively employed in the pharmaceutical industry,12-15 materials science,16 and polymer science.17 In biochemistry, sulfonyl fluorides have been used notably for protease inhibition and as biological probes (Figure 1, Part (a)).18-20 The SuFEx reaction, which occurs between di(arylsulfonyl fluorides) and di(aryl silyl ethers) to produce polysulfonate-SuFEx polymers, has shown remarkable efficiency and holds special significance in polymer science21-24. Traditional methods for synthesizing these functional molecules often require multistep processes (Figure 1, Part (b)). Efficient catalytic processes depend on well-designed and easily accessible precursors. For instance, ethenesulfonyl fluoride (ESF, H2C=CHSO2F) serves as an effective Michael acceptor for creating a variety of nitrogen-, oxygen-, and carbon-based nucleophiles, which are useful in the synthesis of functionalized alkylsulfonyl fluorides (Figure 1, Part (c)).25-27

In this comprehensive evaluation, we spotlight innovative approaches encompassing photoredox catalysis, electrocatalysis, transition-metal-mediated catalysis, and organocatalysis, all of which have emerged as powerful tools for the synthesis of alkylsulfonyl fluorides, as depicted in Figure 1, Part (d).

Figure 1. (a) Chemical Structures of Representative Biologically Active Alkylsulfonyl Fluorides. (b) Conventional Methods Used for the Synthesis of Alkylsulfonyl Fluorides. (c) Sharpless’s Kilogram- Scale Synthesis of ESF. (d) Catalytic Synthetic Methods Highlighted in This Review.

CONCLUSIONS AND OUTLOOK

We have delved into the synthesis of alkylsulfonyl fluorides, encompassing their formation via carbon–carbon and carbon–heteroatom bond formations, along with their fluoride exchange (SuFEx) reactions with suitable coupling agents. The manipulation of the SO2F functional group, enabled by activation techniques such as photoredox catalysis, electrocatalysis, transition-metal catalysis, and organocatalysis, has opened up avenues to an extensive range of both carbocyclic and heterocyclic compounds. We are optimistic that these techniques will enrich the libraries of sulfonyl fluoride-containing compounds, thereby bolstering the research efforts in the fields of pharmaceuticals and agrochemicals.

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