t-BuOK-promoted methylthiolation of aryl fluorides with dimethyldisulfide under transition-metal-free and mild conditions

Huang, Dayun; Wu, Xiangmei

doi:10.1016/j.jfluchem.2021.109778

Cited by 3 publications

(4 citation statements)

References 138 publications

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“…[45] Transition metal free C aryl À F activation using KOtBu also has literature precedence, including activation of C aryl À F bonds via nucleophilic aromatic substitution reactions of aryl halides with amines, either in combination with silylboronate [46] or by itself, [47] as well as C aryl À F fluoride substitution with methyl sulfide. [48] In our system, C aryl À F bonds are not activated; we observe selective activation of a CÀ F bond in trifluoromethyl moieties. Replacing KOtBu with KOH or NaOtBu leads to a significant drop in HDF activity and, in the case of NaOtBu, the appearance of the hydrogen-borrowing product 3a CF3 (Figure 6d).…”

Section: -Vide Infra)mentioning

confidence: 62%

“…For example, complementing known reactivity of alkoxides as reducing agents, [41] KO t Bu was found to facilitate reductive silylation of C−H bonds of heteroaromatic compounds [42–44] and spur the in situ formation of organic electron donors in transition‐metal free reactions [45] . Transition metal free C aryl −F activation using KO t Bu also has literature precedence, including activation of C aryl −F bonds via nucleophilic aromatic substitution reactions of aryl halides with amines, either in combination with silylboronate [46] or by itself, [47] as well as C aryl −F fluoride substitution with methyl sulfide [48] . In our system, C aryl −F bonds are not activated; we observe selective activation of a C−F bond in trifluoromethyl moieties.…”

Section: Resultsmentioning

confidence: 99%

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Tandem Hydrogen‐Borrowing Dehydrogenative Coupling and Hydrodefluorination

Sidhu,

Mondal,

Herbert

2024

Adv Synth Catal

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Dehydrogenative coupling (DC) is an attractive approach to constructing new C‐N bonds using alcohols as electrophiles. In ‘hydrogen‐borrowing’ variants of DC, the H2 liberated can be used to re‐hydrogenate unsaturated intermediates to produce saturated products. Here, we show how so‐generated H2 can also be used to replace fluorine atoms with hydrogens in CF3 groups in a tandem dehydrogenative coupling/hydrodefluorination process.

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Section: -Vide Infra)mentioning

confidence: 62%

Section: Resultsmentioning

confidence: 99%

Tandem Hydrogen‐Borrowing Dehydrogenative Coupling and Hydrodefluorination

Sidhu,

Mondal,

Herbert

2024

Adv Synth Catal

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“…ethyl acetate (chromatography eluent: petroleum ether) was afforded S-methylated product 32 49 (182 mg, 90% yield) as a white solid.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…General methylation procedure A and workup procedure C using CH 2 Cl 2 (20 mL) as the extraction solvent instead of EtOAc (chromatography: petroleum ether) afforded S-methylated product 32 49 (182 mg, 90% yield) as a white solid. 1 H NMR (400 MHz, CDCl 3 ):  = 7.39 (d, J = 8.1 Hz, 2 H), 7.11 (d, J = 8.2 Hz, 2 H), 2.46 (s, 3 H).…”

Section: -Bromo-4-(methylsulfanyl)benzene (32)mentioning

confidence: 99%

A Mild Heteroatom (O-, N-, and S-) Methylation Protocol Using Trimethyl Phosphate (TMP)–Ca(OH)2Combination

Tang

2022

Synthesis

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A mild heteroatom methylation protocol using trimethyl phosphate (TMP)-Ca(OH)2 combination has been developed, which proceeds in DMF, or water, or under neat conditions at 80 oC or at room temperature. A series of O-, N- and S-nucleophiles, including phenols, sulfonamides, N-heterocycles such as 9H-carbazole, indole derivatives, 1,8-naphthalimide, and aryl/alkyl thiols are suitable substrates of this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmental friendly nature of this protocol make it an attractive alternative to the conventional base prompted heteroatom methylation procedures.

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Recent Developments in Selenylation and Thiolation of Alkenes via Three‐component Reactions

Huang

Wang

et al. 2023

Adv Synth Catal

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Alkenes are valuable feedstocks in organic synthesis. Selenium or sulfur-containing coumpounds with a neighboring functional group can be easily prepared by direct difunctionalization of alkenes via three-component reactions. It will reduce the number of steps and waste generation, and form complicated molecules from simple starting materials. Herein, recent developments (2013-2022) have been summarized via two categories: (1) selenylation via seleniranium intermediates or Se-centered radicals;(2) thiolation with more diverse mechanisms and products Reactions with electron-rich arenes, alcohols, water, acids, NaN 3 , amines, KSCN, and sulfamides, TMSNCS, TMSN 3 , Et 3 N • 3HF, SOCl 2 , HCl, NFSI, t BuONO, pyridinium salts, t BuOOH, ArN 2 BF 4 , CO 2 , CO, O 2 , CF 3 SO 2 Cl, R 2 P(O)À H, (RO) 2 P(O)SH, (RO) 2 P(O)OH et al will be discussed.We hope this review will do help for future research in this area.1. Thiolation 3.1. Synthesis of Sulfides 3.2. Synthesis of Sulfoxides 3.3. Synthesis of Sulfones 4.Conclusions and Outlook

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t-BuOK-promoted methylthiolation of aryl fluorides with dimethyldisulfide under transition-metal-free and mild conditions

Cited by 3 publications

References 138 publications

Tandem Hydrogen‐Borrowing Dehydrogenative Coupling and Hydrodefluorination

Tandem Hydrogen‐Borrowing Dehydrogenative Coupling and Hydrodefluorination

A Mild Heteroatom (O-, N-, and S-) Methylation Protocol Using Trimethyl Phosphate (TMP)–Ca(OH)2Combination

Recent Developments in Selenylation and Thiolation of Alkenes via Three‐component Reactions

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