325809-93-6Relevant academic research and scientific papers
A catalytic fluoride-rebound mechanism for C(sp3)-CF3 bond formation
Levin, Mark D.,Chen, Tiffany Q.,Neubig, Megan E.,Hong, Cynthia M.,Theulier, Cyril A.,Kobylianskii, Ilia J.,Janabi, Mustafa,O'Neil, James P.,Toste, F. Dean
, p. 1272 - 1275 (2017)
The biological properties of trifluoromethyl compounds have led to their ubiquity in pharmaceuticals, yet their chemical properties have made their preparation a substantial challenge, necessitating innovative chemical solutions. We report the serendipitous discovery of a borane-catalyzed formal C(sp3)-CF3 reductive elimination from Au(III) that accesses these compounds by a distinct mechanism proceeding via fluoride abstraction, migratory insertion, and C-F reductive elimination to achieve a net C-C bond construction. The parent bis(trifluoromethyl)Au(III) complexes tolerate a surprising breadth of synthetic protocols, enabling the synthesis of complex organic derivatives without cleavage of the Au-C bond. This feature, combined with the fluoride-rebound mechanism, was translated into a protocol for the synthesis of 18F-radiolabeled aliphatic CF3-containing compounds, enabling the preparation of potential tracers for use in positron emission tomography.
Photoinitiated oxidative addition of CF3I to gold(I) and facile aryl-CF3 reductive elimination
Winston, Matthew S.,Wolf, William J.,Toste, F. Dean
, p. 7777 - 7782 (2014/06/10)
Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast Caryl-CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR' (R = Cy, R' = 3,5-F2-C 6H4, 4-F-C6H4, C6H 5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R' = 4-F-C6H4, 4-Me-C6H 4). When R' = aryl, complexes of the type R3PAu(aryl) (CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (λmax = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 °C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor C aryl-I reductive elimination over Caryl-CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu(aryl)(CF3)I results in quantitative formation of Ar-CF3 in less than 1 min at temperatures as low as -10 °C.
C-Si bond cleavage of trihalomethyltrimethylsilane by alkoxo- and aryloxogold or -copper complexes
Usui, Yoko,Noma, Junko,Hirano, Masafumi,Komiya, Sanshiro
, p. 151 - 154 (2008/10/08)
The C-Si bond cleavage of trihalomethyltrimethylsilane Me3SiCX3 (X = F, Cl) proceeds smoothly by alkoxo- and aryloxogold(I or III) or -copper(I) complexes Au(OR)L (OR = OCH(CF3)2, OPh), L =PCy3, PPhs
