119558-77-9Relevant academic research and scientific papers
IMPROVEMENT OF THE SYNTHESIS OF ARYL DIFLUOROMETHYL ETHERS AND THIOEHTERS BY USING A SOLID-LIQUID PHASE-TRANSFER TECHNIQUE
Langlois, Bernard R.
, p. 247 - 262 (1988)
A new solid-liquid phase-transfer technique has been used to synthesize aryl difluoromethyl ehters and thioethers.Phenols (or thiophenols) and chlorodifuoromethane, dissolved in a cheap aprotic solvent of low polarity, are contacted with solid sodium hydroxide in the presence of a catalytic amount of tris-(3,6-dioxaheptyl)amine.The work-up of the reaction mixtures is very simple.Although yields are similar in both homogeneous and heterogeneous procedures using phenols, improved yields are obtained for thiophenols when using phase-transfer conditions.
Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C?H Di- and Trifluoromethoxylation
Lee, Johnny W.,Lim, Sanghyun,Maienshein, Daniel N.,Liu, Peng,Ngai, Ming-Yu
supporting information, p. 21475 - 21480 (2020/10/02)
Applications of TEMPO. catalysis for the development of redox-neutral transformations are rare. Reported here is the first TEMPO.-catalyzed, redox-neutral C?H di- and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional-group tolerance, and can be employed for the late-stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO./TEMPO+ redox catalytic cycle. Mechanistic studies also suggest that Li2CO3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox-neutral TEMPO. catalysis.
Catalytic radical difluoromethoxylation of arenes and heteroarenes
Lee, Johnny W.,Zheng, Weijia,Morales-Rivera, Cristian A.,Liu, Peng,Ngai, Ming-Yu
, p. 3217 - 3222 (2019/03/21)
Intermolecular C-H difluoromethoxylation of (hetero)arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a redox-active difluoromethoxylating reagent 1a and photoredox catalysts for the direct C-H difluoromethoxylation of (hetero)arenes. Our approach is operationally simple, proceeds at room temperature, and uses bench-stable reagents. Its synthetic utility is highlighted by mild reaction conditions that tolerate a wide variety of functional groups and biorelevant molecules. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1a forming a neutral radical intermediate that liberates the OCF2H radical exclusively. Addition of this radical to (hetero)arenes gives difluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of difluoromethoxylation.
DIFLUOROMETHOXYLATION AND TRIFLUOROMETHOXYLATION COMPOSITIONS AND METHODS FOR SYNTHESIZING SAME
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Page/Page column 75; 79; 89; 91, (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.
