402-52-8Relevant articles and documents
Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**
Shreiber, Scott T.,Vicic, David A.
supporting information, p. 18162 - 18167 (2021/07/14)
The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.
NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME
-
Paragraph 0138-0139; 0141-0143, (2021/04/09)
PROBLEM TO BE SOLVED: To provide a method for producing an aromatic perfluoroalkyl compound using silylated trifluoromethyl carbinol. SOLUTION: There is provided a method for producing an aromatic perfluoroalkyl compound represented by the general formula [10], in which a compound represented by the formula [9] and a compound represented by the formula [1] are reacted in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride. R7-X...[9], RF-R7...[10] [In the formula, R7 is an aryl group or the like which may have a substituent; X is F, Cl, Br or I; RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are each independently H or a C1-2 linear alkyl group, or the like; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are each independently H or a C1-2 linear alkyl group, or the like.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
supporting information, p. 15396 - 15405 (2021/10/12)
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.