461-81-4Relevant academic research and scientific papers
A novel synthesis of trifluoromethyl ethers via xanthates, utilizing BrF3
Ben-David, Iris,Rechavi, Dalit,Mishani, Eyal,Rozen, Shlomo
, p. 75 - 78 (1999)
Alcohols were transformed into trifluoromethyl ethers by converting them to xanthates in almost quantitative yields followed by a reaction with bromine trifluoride, a reagent rarely used in organic chemistry.
Radical C?H Trifluoromethoxylation of (Hetero)arenes with Bis(trifluoromethyl)peroxide
Dix, Stefan,Golz, Paul,Schmid, Jonas R.,Riedel, Sebastian,Hopkinson, Matthew N.
supporting information, p. 11554 - 11558 (2021/07/09)
Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C?H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches.
Direct Trifluoromethylation of Alcohols Using a Hypervalent Iodosulfoximine Reagent
Kalim, Jorna,Duhail, Thibaut,Pietrasiak, Ewa,Anselmi, Elsa,Magnier, Emmanuel,Togni, Antonio
supporting information, p. 2638 - 2642 (2021/01/21)
The direct trifluoromethylation of a variety of aliphatic alcohols using a hypervalent iodosulfoximine reagent afforded the corresponding ethers in moderate to good yields (14–72 %). Primary, secondary, and even tertiary alcohols, including examples derived from natural products, underwent this transformation in the presence of catalytic amounts of zinc bis(triflimide). Typical reaction conditions involved a neat mixture of 6.0 equivalents of the alcohol with 1.0 equivalent of the reagent, with the majority of reactions complete within 2 h with 2.5 mol % of the Lewis acid catalyst. Furthermore, experimental evidence was provided that the C?O bond-forming process occurred via the coordination of the alcohol to the iodine atom and subsequent reductive elimination.
Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow
Cendón, Borja,Gulías, Moisés,Ho, Michelle,No?l, Timothy,Nyuchev, Alexander V.,Sambiagio, Carlo,Struijs, Job J. C.,Wan, Ting,Wang, Ying
supporting information, p. 1305 - 1312 (2020/07/10)
The first example of photocatalytic trifluoromethoxylation of arenes and heteroarenes under continuous-flow conditions is described. Application of continuous-flow microreactor technology allowed to reduce the residence time up to 16 times in comparison t
DIFLUOROMETHOXYLATION AND TRIFLUOROMETHOXYLATION COMPOSITIONS AND METHODS FOR SYNTHESIZING SAME
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Page/Page column 43; 46; 56; 57-58, (2019/09/18)
The present invention provides a compound having the structure (I), a processing of making the compound; and a process of using the compound as a reagent for the difluoromethoxylation and trifluoromethoxylation of arenes or heteroarenes.
Visible-Light Photoredox-Catalyzed and Copper-Promoted Trifluoromethoxylation of Arenediazonium Tetrafluoroborates
Yang, Shaoqiang,Chen, Miao,Tang, Pingping
supporting information, p. 7840 - 7844 (2019/05/15)
We report the development of photoredox-catalyzed and copper-promoted trifluoromethoxylation of arenediazonium tetrafluoroborates, with trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxylation reagent. This new method takes advantage of visible-light photoredox catalysis to generate the aryl radical under mild conditions, combined with copper-promoted selective trifluoromethoxylation. The reaction is scalable, tolerates a wide range of functional groups, and proceeds regioselectively under mild reaction conditions. Furthermore, mechanistic studies suggested that a Cs[Cu(OCF3)2] intermediate might be generated during the reaction.
Redox-Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero)Aryl C?H Trifluoromethoxylation
Zheng, Weijia,Lee, Johnny W.,Morales-Rivera, Cristian A.,Liu, Peng,Ngai, Ming-Yu
supporting information, p. 13795 - 13799 (2018/09/27)
The trifluoromethoxy (OCF3) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox-active cationic reagent (1) that enables the formation of the OCF3 radical in a controllable, selective, and catalytic fashion under visible-light photocatalytic conditions is reported. More importantly, the reagent allows catalytic, intermolecular C?H trifluoromethoxylation of a broad array of (hetero)arenes and biorelevant compounds. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1 resulting in exclusive liberation of the OCF3 radical. Addition of this radical to (hetero)arenes gives trifluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of trifluoromethoxylation.
Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N?O Bond Redox Fragmentation
Jelier, Benson J.,Tripet, Pascal F.,Pietrasiak, Ewa,Franzoni, Ivan,Jeschke, Gunnar,Togni, Antonio
supporting information, p. 13784 - 13789 (2018/09/14)
A simple trifluoromethoxylation method enables non-directed functionalization of C?H bonds on a range of substrates, providing access to aryl trifluoromethyl ethers. This light-driven process is distinctly different from conventional procedures and occurs through an OCF3 radical mechanism mediated by a photoredox catalyst, which triggers an N?O bond fragmentation. The pyridinium-based trifluoromethoxylation reagent is bench-stable and provides access to synthetic diversity in lead compounds in an operationally simple manner.
Catalytic C?H Trifluoromethoxylation of Arenes and Heteroarenes
Zheng, Weijia,Morales-Rivera, Cristian A.,Lee, Johnny W.,Liu, Peng,Ngai, Ming-Yu
supporting information, p. 9645 - 9649 (2018/03/21)
The intermolecular C?H trifluoromethoxylation of arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox-active catalysts for the direct (hetero)aryl C?H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy-to-handle reagents, requires only 0.03 mol % of redox-active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground-state and photoexcited redox-active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF3 radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox-active catalysts and deprotonated to form the desired products of trifluoromethoxylation.
Trifluoromethyl Benzoate: A Versatile Trifluoromethoxylation Reagent
Zhou, Min,Ni, Chuanfa,Zeng, Yuwen,Hu, Jinbo
supporting information, p. 6801 - 6805 (2018/05/31)
Trifluoromethyl benzoate (TFBz) is developed as a new shelf-stable trifluoromethoxylation reagent, which can be easily prepared from inexpensive starting materials using KF as the only fluorine source. The synthetic potency of TFBz is demonstrated by trifluoromethoxylation-halogenation of arynes, nucleophilic substitution of alkyl (pseudo)halides, cross-coupling with aryl stannanes, and asymmetric difunctionalization of alkenes. The unprecedented trifluoromethoxylation-halogenation of arynes proceeds smoothly at room temperature with the aid of a crown ether-complexed potassium cation, which significantly stabilizes the trifluoromethoxide anion derived from TFBz.
