Organic molecules containing fluorine have attracted much attention because they show distinctive characteristics in comparison with their parent compounds owing to the unique CÀF bond. [1] Substitution of hydrogen by fluorine is often considered isosteric and the high C À F bond strength generally protects fluorine from metabolic transformations. In addition, as fluorine has the ability to function as a hydrogen bond acceptor, fluorine-substituted bioactive compounds are useful analogues and probes of hydrogen bonding characteristics. The selective formation of carbon-fluorine bonds under mild conditions is thus a highly desirable methodology, especially in medicinal chemistry. [2] Previous approaches toward asymmetric fluorination relied on stoichiometric amounts of chiral fluorinating reagents [3] or chiral auxiliaries. [4] More recently, the catalytic asymmetric fluorination of b-keto esters with titanium and palladium as Lewis acids was reported. [5] a-Fluoro aldehydes have been characterized as unstable compounds that generally decompose upon purification. As a result, their syntheses have been very limited. Synthesis of afluoro aldehydes was first reported by Middleton and Bingham, who treated silyl enol ethers with trifluoromethyl hypofluorite (CF 3 OF). [6] Subsequently, enolate methodologies that use commercially available electrophilic fluorinating reagents such as NFSi (N-fluorobenzenesulfonamide; 5) and Selectfluor (F-TEDA-BF 4 or 1-chloromethyl-4-fluoro-1,4diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate); 3) have