In spite of only a few naturally occurring products having one or more fluorine atoms, organofluorine compounds have been widely utilized in pharmaceutical, agrochemical, and functional material science fields due to the characteristic properties of the fluorine atom. Therefore, the development of new methods for the introduction of fluorine-containing functional groups has been a long-standing research topic. This article discusses our contributions to this area. The first topic is on the trifluoromethylations of C-C multiple bonds using Togni reagent based on our working hypothesis that hypervalent iodine could be activated by coordination of the carbonyl moiety to the Lewis acid catalyst. The second topic relates to asymmetric fluorofunctionalization of alkenes. A newly designed phase-transfer catalyst consisting of a carboxylate anion functioning as a phase-transfer agent and a primary hydroxyl group as a site that captures the anionic substrate was revealed to be an effective catalyst for asymmetric fluorolactonization. Inspired by the mechanistic studies of fluorolactonization, we produced a linked binaphthyl dicarboxylate catalyst, which catalyzes the 6-endo-fluorocyclization and the deprotonative fluorination of allylic amides in a highly enantioselective manner. The third topic is on C-H fluorofunctionalizations using either catalysis or photoactivation. Benzylic trifluoromethylation, which is still a rare reaction, using Togni reagent and aromatic C-H trifluoromethylation using Umemoto reagent under simple photoirradiation conditions were achieved. In addition, the Csp3-H fluorination of alkyl phthalimide derivatives is demonstrated.
Keywords: C–H functionalization; alkene double functionalization; catalyst; fluorine; trifluoromethyl group.