Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions

Abstract

Fluorine is the most electronegative element in the periodic table, and the introduction of one or more fluorine atoms into a molecule can result in greatly perturbed properties. Methods to introduce fluorine into small organic molecules have been actively investigated for many years by specialists in the field of fluorine chemistry. The earliest advances in catalytic asymmetric fluorination were made by exploiting transition metal enolates, capable of a bidentate mode of coordination to a metal. In 2002, Sodeoka and coworkers reported the enantioselective fluorination of β-ketoesters catalyzed by a chiral palladium complex. In 2005, Shibata and co-workers reported enantioselective chlorination and fluorination of carbonyl compounds capable of two-point binding. In 2011, Gade and co-workers described the synthesis of a new class of chiral tridentate N-donor pincer ligands, bis(oxazolinyl-methyldiene)isoindolines.