Direct trifluoromethylthiolation of aryl halides using methyl fluorosulfonyldifluoroacetate and sulfur

Chen, Qing‐Yun; Duan, Jian‐Xing

doi:10.1039/c39930000918

Cited by 91 publications

(30 citation statements)

References 6 publications

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“…Aryl trifluoromethyl sulfides have been synthesized from aryl diazonium salts (Scheme )480 and electron‐poor aryl iodides (Scheme )481 by Clark and co‐workers by reaction with pregenerated copper trifluoromethylthiolate. Chen and Duan have reported the in situ generation of copper trifluoromethylthiolate at 100 °C from copper, sulfur (S 8 ), and fluorosulfonyldifluoroester for the trifluoromethylthiolation of aryl iodides 482…”

Section: Trifluoromethyl Ethers Sulfides and Aminesmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,303

856

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Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo‐ and transition‐metal catalysis. The most challenging transformation remains the formation of the parent CF bond, primarily as a consequence of the high hydration energy of fluoride, strong metal—fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost‐efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Section: Trifluoromethyl Ethers Sulfides and Aminesmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,303

856

View full text Add to dashboard Cite

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“…The synthetic pathway used in our study to prepare 3 is outlined in Scheme 2. In a first attempt, we aimed to synthesize 3 in a single reaction step by applying a modified procedure reported by Chen et al,28 namely by treatment of 1a with S 8 , copper(I) iodide and methyl fluorosulfonyldifluoroacetate in N-methylpyrrolidinone (NMP) at 100 °C overnight. These conditions only led to the formation of trace amounts of 3.…”

Section: Resultsmentioning

confidence: 99%

Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Substituted Metallocenes

et al. 2014

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A novel synthetic pathway for trifluoromethylthioferrocene (3), which does not involve the use of toxic mercury(II)-based reagents, is described. The novel approach involves first the treatment of the commercially available bromoferrocene (1a) with NaSCN in the presence of copper(+I) to yield thiocyanatoferrocene (1), and then the reaction of 1 with the Rupper-Prakash reagent and tetrabutylammonium fluoride (TBAF) to give 3 in an overall yield of 60%. This approach could be extended for the preparation of thiocyanato-(4) and trifluoromethylthio-ruthenocene (7), which are herein both reported for the first time. Interestingly, diferrocenyl disulfide (2a) and diruthenocenyl disulfide (5) could be isolated as side-products during the synthesis of 3 and 7, respectively. All new compounds were unambiguously characterized by (1)H, (13)C, and (19)F NMR spectroscopy, mass spectrometry, cyclic voltammetry, elemental analysis, as well by X-ray crystallography for 1, 4, 4b, 5, 6, and 7. 1-7 were further tested for their toxic activity on cervical cancer (HeLa) and noncancerous (MRC-5) cell lines. All organometallic compounds were found either to be nontoxic or to have a moderate toxicity toward the cell lines used in this study. ABSTRACT: A novel synthetic pathway for trifluoromethylthioferrocene (3), which does not involve the use of toxic mercury(II)-based reagents, is described. The novel approach involves first the treatment of the commercially available bromoferrocene (1a) with NaSCN in the presence of copper(+I) to yield thiocyanatoferrocene (1), and then the reaction of 1 with the Rupper-Prakash reagent and tetrabutylammonium fluoride (TBAF) to give 3 in an overall yield of 60%. This approach could be extended for the preparation of thiocyanato-(4) and trifluoromethylthio-ruthenocene (7), which are herein both reported for the first time. Interestingly, diferrocenyl disulfide (2a) and diruthenocenyl disulfide (5) could be isolated as side-products during the synthesis of 3 and 7, respectively. All new compounds were unambiguously characterized by 1 H, 13 C and 19 F NMR spectroscopy, mass spectrometry, cyclic voltammetry, elemental analysis as well by X-ray crystallography for 1, 4, 4b, 5, 6 and 7. 1-7 were then tested for their toxic activity on a cervical cancer (HeLa) and on a non-cancerous (MRC-5) cell lines. All organometallic compounds were found to be either not toxic or to have a moderate toxicity towards the cell lines used in this study.

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“…Otherwise, trifluoromethyl phenyl thioethers and ring-substituted analogs are readily made from iodo-or bromoarenes, methyl difluoro(fluorosulfonyl)acetate and elemental sulphur in the presence of cuprous iodide in hexamethylphosphoric triamide (HMPA) or N-methylpyrrolidone (NMP) as depicted in Scheme 47 [152].…”

Section: A-trifluoromethyl Thioethersmentioning

confidence: 99%

New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines

Manteau

Pazenok

Vors

et al. 2010

Journal of Fluorine Chemistry

365

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Direct trifluoromethylthiolation of aryl halides using methyl fluorosulfonyldifluoroacetate and sulfur

Abstract: In the presence of S8 and copper(i) iodide, methyl fluorosulfonyldifluoroacetate 1 reacts with aryl halides 2 in hexamethylphosphoramide (HMPA) or N-methylpyrrolidinone (NMP) at 100-1 10 "C to give the corresponding trifluoromethylthiolated derivatives 3 in good yields.

Cited by 91 publications

References 6 publications

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Substituted Metallocenes

New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines

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