Sandmeyer‐Trifluormethylierung von Aryldiazoniumtetrafluorboraten

Abstract

Cu in der Vermittlerrolle: In Anwesenheit eines in situ aus Kupferthiocyanat und dem preiswerten, leicht handhabbaren Trifluormethylierungsreagens Me3Si‐CF3 erzeugten Trifluormethyl‐Kupfer‐Komplexes können Diazoniumsalze direkt in ihre entsprechenden Trifluormethylderivate überführt werden (siehe Schema). Diese Variante der Sandmeyer‐Reaktion ermöglicht die direkte Synthese trifluormethylierter Arene und Heteroarene ausgehend von Aminen.

The Trifluoromethylating Sandmeyer Reaction: A Method for Transforming CN into CCF3

“…Towards this goal, recently, the scope of potential starting materials has been dramatically increased. The groups of Wang,7 Gooßen,8 and Fu9 have reported the CN to CCF 3 transformation using a trifluoromethylating Sandmeyer reaction, as outlined herein.…”

Site‐Specific Deaminative Trifluoromethylation of Aliphatic Primary Amines**

“…First, the influence of blue light irradiation on the reaction was explored. As depicted in Scheme 3a, the photolysis of complex 5 with blue light in the presence of 2,2,6,6-tetramethylpiperidineoxy (TEMPO) afforded the TEMPO-CF 3 adduct 6 in 60 % yield (as determined by 19 F NMR), whereas no detectable formation of 6 was observed without light. This outcome suggests the generation of trifluoromethyl radical from bpyCu(CF 3 ) 3 upon photostimulation.…”

One‐Pot Sandmeyer Trifluoromethylation and Trifluoromethylthiolation

“…As an alternative to these methods, Sandmeyer‐type trifluoromethylations were almost simultaneously disclosed by Fu,25 Wang26 and ourselves27 (Scheme ). Their key advantage is that they draw on aromatic amines, widely available in great structural diversity, as the aryl source 28.…”