SuFEx (Sulfur Fluoride Exchange) is a modular, next generation family of click reactions, geared towards the rapid and reliable assembly of functional molecules. This review discusses the growing number of applications of SuFEx, which can be found in nearly all areas of modern chemistry; from drug discovery to materials science.

The growing applications of SuFEx click chemistry

This review describes the recent developments in the field of Suzuki-Miyaura cross-coupling reaction, in particular with regard to ligand-free catalysis. The catalysts outlined here allow convenient and green synthetic pathways specifically for the construction of C-C bonds. They enable the synthesis of biaryls by the coupling arylboronic acids with aryl halides. The literature reporting ligand-free synthesis of biaryls from 2010 to May 2015 has been reviewed.

Synthesis of Biaryls via Ligand‐Free Suzuki–Miyaura Cross‐Coupling Reactions: A Review of Homogeneous and Heterogeneous Catalytic Developments

Sulfur(VI) fluoride exchange (SuFEx) is a new family of click chemistry based transformations that enable the synthesis of covalently linked modules via SVI hubs. Here we report thionyl tetrafluoride (SOF4 ) as the first multidimensional SuFEx connector. SOF4 sits between the commercially mass-produced gases SF6 and SO2 F2 , and like them, is readily synthesized on scale. Under SuFEx catalysis conditions, SOF4 reliably seeks out primary amino groups [R-NH2 ] and becomes permanently anchored via a tetrahedral iminosulfur(VI) link: R-N=(O=)S(F)2 . The pendant, prochiral difluoride groups R-N=(O=)SF2 , in turn, offer two further SuFExable handles, which can be sequentially exchanged to create 3-dimensional covalent departure vectors from the tetrahedral sulfur(VI) hub.

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Multidimensional SuFEx Click Chemistry: Sequential Sulfur(VI) Fluoride Exchange Connections of Diverse Modules Launched From An SOF4 Hub.

Sulfuryl fluoride, SO2 F2 , has been found to derivatize phenols in all kinds of environments, even those in highly functional molecules. We now report that a solid fluorosulfuryl imidazolium triflate salt delivers the same "F-SO2 +" fragment to Nu-H acceptor groups in the substrates. However, this triflate salt is a far more reactive fluorosulfurylating agent than SO2 F2 and displays selectivity preferences of its own. Moreover, the new azolium triflate reagent reacts once with primary amines and anilines before the reaction stops. On the other hand, with triethylamine and two equivalents of the "F-SO2 +" donor present, it proceeds on to the bis(fluorosulfuryl)imides in good yield-two important conversions that we have never seen with sulfuryl fluoride as the electrophile.

A New Portal to SuFEx Click Chemistry: A Stable Fluorosulfuryl Imidazolium Salt Emerging as an “F−SO2+” Donor of Unprecedented Reactivity, Selectivity, and Scope

We report the development of palladium(0)-catalyzed syn-selective 1,2-carboboration and -silylation reactions of alkenes containing cleavable directing groups. With B2 pin2 or PhMe2 Si-Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono-, di-, tri- and tetrasubstituted alkenes are compatible in these transformations. We further describe a directed dearomative 1,2-carboboration of electron-rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck-type alkene 1,2-difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio- and stereocontrol.

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Palladium-catalyzed, ligand-free Suzuki reaction in water using aryl fluorosulfates.

Easily prepared aryl fluorosulfates are used as coupling partners in the Suzuki—Miyaura reaction.

Qiaobin Liang

Papers

Palladium-catalyzed, ligand-free Suzuki reaction in water using aryl fluorosulfates.

Palladium‐Catalyzed, Ligand‐Free Suzuki Reaction in Water Using Aryl Fluorosulfates.