Development and Application of <i>O</i>-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes

Qiao, Chunming; Yu, Gino; Xu, Zhaoqing; Lin, Li; Jiang, Xianxing; Wang, Rui

doi:10.1021/acs.joc.5b00923

Cited by 37 publications

(23 citation statements)

References 62 publications

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“…[29,30] Fluorosulfonates, also known as "super sulfates," were first reported more than four decades ago, [31][32][33][34][35][36] their chemistry, however, is relatively unexplored. [29,30] Fluorosulfonates, also known as "super sulfates," were first reported more than four decades ago, [31][32][33][34][35][36] their chemistry, however, is relatively unexplored.…”

Section: Introductionmentioning

confidence: 99%

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

Wang

et al. 2019

Advanced Science

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are encoded by unique DNA sequences as identification "barcodes," and are assembled combinatorial using split-andpool strategy or alternative procedures via DNA-compatible reactions. [7][8][9] DELs comprising millions or even billions of DNA-tagged druglike molecules can be effectively synthesized via this technology and screened against various protein targets of interest in a single pooled assay. In a typical affinity-based selection experiment, when non-and low-affinity binders are washed away, the DNA tag of the remaining compounds can be amplified using polymerase chain reaction and the relative frequency of the remaining compounds before and after selection is determined by counting the number of DNA tags in high-throughput DNA sequencing experiments. [10,11] To date, a large number of high-quality hits have been identified by the DEL technology for various therapeutically relevant targets, such as kinases, [12] phosphatases, [13] and G-protein coupled receptors. [14] Several drug candidates derived from their corresponding DEL hits, such as soluble epoxide hydrolase inhibitor GSK2256294, and death domain receptor-associated adaptor kinase RIP1 inhibitor GSK2982772 have progressed to latestage clinical development, [15,16] further emphasizing DEL as a powerful technology for small molecular drug discovery.Despite these successes, the great potential of DEL technology in drug discovery has not yet been fully realized. One of the most fundamental challenges is the synthesis of high-quality libraries with more structural diversity, which in turn depends on the development of new and robust DNA-compatible reactions that allow more flexibility in DEL's design and synthesis. Among various DNA-compatible reactions developed in recent years, transition-metal-promoted reactions such as Suzuki-Miyaura coupling, [17][18][19][20][21][22][23] Sonogashira coupling, and Buchwald-Hartwig amination using DNA-conjugated aryl halides as electrophiles have been elegantly developed (Figure 1), [24][25][26] and some of them have been developed for DEL synthesis. However, the environmental toxicity and high costs of aryl halides have hindered their large-scale applications in industry. Thus, much attention has been paid to phenol-derived electrophiles recently, [27] which, as compared to aryl halides, offer a more sustainable starting material because most of them are readily available from biomass. [28] In addition, phenol modules are also important components of natural products (NPs), bioactive molecules, and pharmaceutical drugs. Coupling reactions with Using (hetero)aryl fluorosulfonates as versatile electrophiles, facile on-DNA cross-coupling reactions of Suzuki, Sonogashira, and Buchwald are reported here. Notably, all of these reactions show excellent functional group tolerance, mild reaction conditions (relative low temperature and open to air), rich heterocyclic coupling partners, and more importantly, DNA-compatibility. Thus, these new reactions based on efficient formation of C(sp 2 )-C(sp 2 ), C(sp 2 )-C(sp), and C(s...

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Section: Introductionmentioning

confidence: 99%

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

Wang

et al. 2019

Advanced Science

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“…has been successfully applied in the construction of C(sp 2 )ÀC and C(sp 2 ) À Nb onds. [10] SO 2 F 2 has also been applied in the production of the important yet expensive bis(fluorosulfuryl)imide anion for the new-generation electrolyte in lithium ion batteries. [11] Although SO 2 F 2 possesses ideal reactivity and selectivity as aS uFEx connector,i te ncountered several challenges as areagent for use in research laboratories.First, operations are problematic for those laboratories without sufficient apparatus to handle harmful gas or under strict regulations to acquire SO 2 F 2 .S econd, compared with phenols,S O 2 F 2 reacted sluggishly with secondary amines to generate sulfamoyl fluorides with al imited substrate scope,a nd complicated reaction conditions were required.…”

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confidence: 99%

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

Guo,

Meng,

Zhan

et al. 2018

Angew Chem Int Ed

179

126

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Sulfuryl fluoride, SO F , 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-SO +" fragment to Nu-H acceptor groups in the substrates. However, this triflate salt is a far more reactive fluorosulfurylating agent than SO F 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-SO +" 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.

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“…Wang and co‐workers reported that o ‐(trimethylsilyl) phenyl fluorosulfate ( 150 ) reacted with different azides that contained electron‐donating as well as electron‐withdrawing substituents under their optimized reaction conditions to afford benzotriazoles 151 in good‐to‐excellent yields (Scheme ) . The same group also continued their research to expand the synthetic applicability of this precursor to other types of reactions (Scheme ).…”

Section: Chemical Transformationsmentioning

confidence: 99%

Synthesis and Chemical Transformations of Fluorosulfates

Lekkala

Leng

et al. 2018

Asian J Org Chem

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Fluorosulfates are readilya vailablee lectrophiles that can be prepared from the reactions of phenol or alcohol derivatives with sulfuryl fluoride, fluorosulfonic acid, sulfuryl chloridef luoride, and fluorosulfonic anhydride. This Focus Review coversm ost of the synthetic strategies that have been reported for the construction of fluorosulfates,a s well as their application as versatile buildingb locks in av ariety of synthetic transformations, such as catalyzed amination, cross-coupling, sulfur(VI) fluoridee xchange, carbonylation, hydrolysis, alcoholysis,a nd as alternatives to organic halidesort riflates in organic chemistry.Scheme79. Synthesis of g-pyrone by using fluorosulfate 34.Scheme80. Reactions of fluorosulfatesw ith nucleophilicreagents.Scheme81. Synthesis of the desired allenefrom fluorosulfate 68. Scheme82. Preparation of benzenef rom phenyl fluorosulfate (110).Scheme83. Synthesis of compound 170 from fluorosulfate 169.

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Development and Application of O-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes

Cited by 37 publications

References 62 publications

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

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

Synthesis and Chemical Transformations of Fluorosulfates

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Development and Application of O-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes

Cited by 37 publications

References 62 publications

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

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

Synthesis and Chemical Transformations of Fluorosulfates

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