Triflamides synthesis

An alternative to Gabriel synthesis is based on the alkylation of tnfluoro-acetamide [770, 777[ or Al-benzyl triflamide [772] in place of the classical phtalimide (equations 96 and 97). 

Amides of trifluoromethanesulfonic acid (triflamides) can be prepared by the reaction of the corresponding amines with triflic anhydnde The most applicable m organic synthesis are N-phenyltnflamides, which can be used as mild and selective inflating reagents [UO, III]... 

Synthesis of 345 has been achieved (equation 221) by reaction of [18F]fluoride with the triflamide alcohol 342 or via the cyclic sulphamate 344. 

Polymeric catalysts. A very useful modification of the catalyst is obtained by ligand exchange with a (polyallyl)triflamide, forming polymer-bound scandium triflamide bistriflate. The catalyst has been used in the combinatorial synthesis of a tetrahydroquinoline library from anilines, aldehydes, and alkenes. A related catalyst prepared from ScClj-bHjO and Nafion is effective in several useful synthetic reactions, including allylation, Diels-Alder reaction, and Friedel-Crafts acylation. ... 

In a recent modification, Yu et al. described a Pd-catalyzed C-H activation/ orf/to-fluorination of triflamide-protected benzylamines with W-fluoro-2,4,6-collidinium cation (Scheme 19) [50]. The authors found that to achieve high yields it was cmcial to use small amounts of NMP as a promoter. As the triflamide group can be easily converted to many other functional groups, such as aldehydes or azides, the reported method allows for an efficient synthesis of various ortho-fluorinated aromatic products. 

Triflamides can be deprotected reductively (Sodium-Ammonia) to yield the corresponding amines.This protocol has been employed in the facile two-step synthesis of aza macrocycles starting from trifluoromethanesulfonyl derivatives of linear tetramines (eq 8). ... 

These conditions are sufficiently mild to allow the synthesis of a triflamide from the corresponding oxetane 0-TMS ether (eq 9), although subsequent attempted removal of the trifiate using LiAlH4 destroyed the oxetane. 

Aniline allowed to react at -78° with trifluoromethanesulfonic acid anhydride and triethylamine in methylene diloride -> N-phenyltriflamide. Y 97%. - The protective group can be removed by reduction. F. e. and triflating agent, also Gabriel-type synthesis of prim, amines from halides via triflamides, s. J. B. Hendrickson and R. Bergeron, Tetrah. Let. 1973, 3839. 

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