551936-59-5Relevant articles and documents
The merger of decatungstate and copper catalysis to enable aliphatic C(sp 3)–H trifluoromethylation
Sarver, Patrick J.,Bacauanu, Vlad,Schultz, Danielle M.,DiRocco, Daniel A.,Lam, Yu-hong,Sherer, Edward C.,MacMillan, David W. C.
, p. 459 - 467 (2020/03/23)
The introduction of a trifluoromethyl (CF3) group can dramatically improve a compound’s biological properties. Despite the well-established importance of trifluoromethylated compounds, general methods for the trifluoromethylation of alkyl C–H bonds remain elusive. Here we report the development of a dual-catalytic C(sp3)–H trifluoromethylation through the merger of light-driven, decatungstate-catalysed hydrogen atom transfer and copper catalysis. This metallaphotoredox methodology enables the direct conversion of both strong aliphatic and benzylic C–H bonds into the corresponding C(sp3)–CF3 products in a single step using a bench-stable, commercially available trifluoromethylation reagent. The reaction requires only a single equivalent of substrate and proceeds with excellent selectivity for positions distal to unprotected amines. To demonstrate the utility of this new methodology for late-stage functionalization, we have directly derivatized a broad range of approved drugs and natural products to generate valuable trifluoromethylated analogues. Preliminary mechanistic experiments reveal that a ‘Cu–CF3’ species is formed during this process and the critical C(sp3)–CF3 bond-forming step involves the copper catalyst. [Figure not available: see fulltext.].
Copper-catalyzed intermolecular trifluoromethylazidation of alkenes: Convenient access to CF3-containing alkyl azides
Wang, Fei,Qi, Xiaoxu,Liang, Zhaoli,Chen, Pinhong,Liu, Guosheng
supporting information, p. 1881 - 1886 (2014/03/21)
A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF 3-containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3- containing amine derivatives. The title reaction proceeds with a CF 3+ reagent under mild reaction conditions. This transformation presents a broad substrate scope and good functional-group tolerance. A variety of CF3-containing organoazides are directly synthesized from a wide range of olefins, including activated and unactivated alkenes. The resulting products are easily transformed into the corresponding amine derivatives. Copyright
