Nucleophilic displacements of non-racemic α-trifluoromethyl benzylic triflates

Photoredox‐Coupled F‐Nucleophilic Addition: Allylation of gem‐Difluoroalkenes

“…In this respect, while the exploration of new synthetic methods for the assembly of CF 3 ‐substituted aromatic framework constituted a flourishing direction,– progress in the development of strategies for the construction of benzylic CF 3 ‐embeded tertiary/quarternary carbon centers lagged behind . Aside from a handful of CF 3 ‐radical‐based functionalizations of structurally elaborated styrene derivatives, these molecules could be created either by direct trifluoromethylation of aliphatic skeletons or through cross‐coupling using α‐CF 3 ‐derived precursors (Scheme a) . With Li's pioneering work on trifluoromethylation of alkyl radicals using Grushin's reagent, the groups of MacMillan, Cook, and Liu, developed decarboxylative and benzylic C−H trifluoromethylation protocols, although the employment of expensive CF 3 reagents, as well as restricted substrate scope, are still concerns.…”

“…[3] Aside from ah andful of CF 3 -radical-based functionalizations of structurally elaborated styrene derivatives, [4] these molecules could be created either by direct trifluoromethylation of aliphatic skeletons [5] or through crosscoupling using a-CF 3 -derived precursors (Scheme 1a). [6,[12][13][14][15][16] With Lisp ioneering work on trifluoromethylation of alkyl radicals using Grushinsreagent, [7] thegroups of MacMillan, [8] Cook, [9] and Liu, [10] developed decarboxylative and benzylic C À Ht rifluoromethylation protocols,a lthough the employment of expensive CF 3 reagents,aswell as restricted substrate scope,are still concerns.…”

Tuning a modular system – synthesis and characterisation of a boron-rich s-triazine-based carboxylic acid and amine bearing a galactopyranosyl moiety

“…A similar reaction was observed by Hughes et al when reacting α-trifluoromethyl benzyl triflates with octanoic acid. 40 These observations led to a different synthetic approach (Scheme 2). Starting from cyanuric chloride and tert-butyl glycinate hydrochloride the dichloro species tert-butyl(4,6dichloro-1,3,5-triazin-2-yl)glycinate (7) was prepared to introduce a protected carboxylic acid group and thus avoid the side reaction leading to 6 (Scheme 1, step d).…”

A Coumarin Triflate Reagent Enables One‐Step Synthesis of Photo‐Caged Lipid Metabolites for Studying Cell Signaling

“…However, benzylic or allylic triflates are not typically used in nucleophilic substitution reactions featuring carboxylate or phosphate nucleophiles. In fact, to the best of our knowledge, only one such example has been reported for a carboxylate nucleophile and none for phosphates. We proceeded to synthesize 1 starting from the corresponding coumarin alcohol.…”

“…In fact, to the best of our knowledge, only one such example has been reported for ac arboxylate nucleophile [27] and none for phosphates.W ep roceeded to synthesize 1 starting from the corresponding coumarin alcohol. However,b enzylic or allylic triflates are not typically used in nucleophilic substitution reactions featuring carboxylate or phosphate nucleophiles.…”