Novel Bifunctionalization of Activated Methylene: Base‐Promoted Trifluoromethylthiolation of β‐Diketones with Trifluoromethanesulfinyl Chloride

Sun, Dongwei; Jiang, Min; Liu, Jintao

doi:10.1002/chem.201901781

Cited by 19 publications

(6 citation statements)

References 65 publications

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“…To address this shortcoming, in recent years, electrophilic trifluoromethylathiolation using trifluoromethylsulfonyl chloride, trifluoromethylsulfinate salts, or trifluoromethylsulfinyl chloride has been reported (Scheme ). Some of these reagents are commercially available. However, a reducing reagent such as phosphine is generally required to generate in situ the reactive species, thus rendering their limited substrate scope.…”

Section: Summary and Perspectivementioning

confidence: 99%

A Toolbox of Reagents for Trifluoromethylthiolation: From Serendipitous Findings to Rational Design

Shen

2023

J. Org. Chem.

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Two types of electrophilic trifluoromethylthiolating reagents were developed in the past 10 years in our laboratory. The development of the first type of reagent, trifluoromethanesulfenate I, which is highly reactive toward a variety of nucleophiles, was based on an unexpected discovery in the initial design for the development of an electrophilic trifluoromethylthiolating reagent with a hypervalent iodine skeleton. A structure−activity study disclosed that α-cumyl trifluoromethanesulfenate (reagent II) without the iodo substituent is equally effective. Subsequent derivatization let us develop an α-cumyl bromodifluoromethanesulfenate III that could be used for the preparation of [ 18 F]ArSCF 3 . To remediate the low reactivity of the type I electrophilic trifluoromethylthiolating reagent for Friedel−Crafts trifluoromethylthiolation of electron-rich (hetero)arenes, we designed and prepared N-trifluoromethylthiosaccharin IV, which exhibits broad reactivity toward various nucleophiles, including electron-rich arenes. A comparison of the structure of N-trifluoromethylthiosaccharin IV with that of N-trifluoromethylthiophthalimide showed that the replacement of one carbonyl group in N-trifluoromethylthiophthalimide with a sulfonyl group made Ntrifluoromethylthiosaccharin IV much more electrophilic. Thus, the replacement of both carbonyls with two sulfonyl groups would further increase the electrophilicity. Such a rationale prompted us to design and develop the current most electrophilic trifluoromethylthiolating reagent, N-trifluoromethylthiodibenzenesulfonimide V, and its reactivity was much higher than that of Ntrifluoromethylthiosaccharin IV. We further developed an optically pure electrophilic trifluoromethylthiolating reagent, (1S)-(−)-Ntrifluoromethylthio-2,10-camphorsultam VI, for the preparation of optically active trifluoromethylthio-substituted carbon stereogenic centers. Reagents I−VI now constitute a powerful toolbox for the introduction of the trifluoromethylthio group into the target molecules.

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Section: Summary and Perspectivementioning

confidence: 99%

A Toolbox of Reagents for Trifluoromethylthiolation: From Serendipitous Findings to Rational Design

Shen

2023

J. Org. Chem.

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“…When there are ortho-hydroxyl or ortho-amino substituents on the phenyl group of β -diketones, the corresponding trifluoromethylthiolated cyclization products were obtained (Scheme 19). 37 Scheme 19 Related reports on the trifluoroalkylthiolation with CF3SOCl.…”

Section: Synlett Account / Synpactsmentioning

confidence: 99%

Direct Fluoroalkylthiolation Based on Fluoroalkanesulfite Derivatives

Wei

Liang

Jiang

et al. 2023

Synlett

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Fluoroalkylthio groups have received substantial attention in the past decade because of their unique physicochemical characteristics, and methods for incorporating these substituents into organic molecules have been rapidly developed in recent years. This account summarizes our efforts on the development of direct fluoroalkylthiolation with fluoroalkanesulfite derivatives, several innovative and efficient strategies for the fluoroalkylthiolation of various substrates have been disclosed, affording various valuable fluoroalkylthiolated compounds in good yields.

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“…Under similar conditions, the reaction with ClCF 2 CF 2 SO 2 Na, n-C 4 F 9 SO 2 Na and n-C 6 F 13 SO 2 Na in the presence of phosphorus oxychloride gave the corresponding 2-aryl-3-(perfluoroalkylthio)-4H-chromen-4-ones, in modest yields (Scheme 66). 383…”

Section: Scheme 64mentioning

confidence: 99%