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- W2020120897 endingPage "829" @default.
- W2020120897 startingPage "817" @default.
- W2020120897 abstract "Trifluomethylated organic compounds often have properties that make them suitable for diverse applications, including materials science, agrochemistry, and pharmaceutical industry. But of all the therapeutic drugs currently available, about 10% of them have a partially fluorinated moiety. Thus, a great deal of attention is being paid to the development of reliable methodologies for trifluoromethylation. Introduction of a trifluoromethyl group into the target molecules mostly relies on either trifluoromethylating reagents or trifluoromethylated synthetic blocks. The chemistry of trifluoromethyl carbanions, nucleophilic trifluoromethylating agents such as the Ruppert−Prakash reagent, and organometallic species has been intensively developed for their important synthetic applications. But the chemistry of β,β,β-trifluoroethyl carbanions (α-trifluoromethyl carbanions) and organometallic species has remained undeveloped despite their potential usefulness in organic synthesis. The issue needs to be addressed. This Account outlines successful alkylations and useful synthetic applications of α-trifluoromethyl carbanions, such as α-substituted β,β,β-trifluoroethyl, α-trifluoromethylethenyl, trifluoroacetimidoyl, α-trifluoromethyloxiranyl, and related α-trifluoromethylated carbanions. The strong electron-withdrawing effect of the α-trifluoromethyl group may stabilize the carbanion species electronically. But α-trifluoromethyl carbanions and their corresponding organometallic species mostly release fluoride spontaneously to produce difluoroalkenes. This notorious decomposition of α-trifluoromethylated carbanions and anionoids has hindered the development of these species for organic synthesis. A well-designed device for the generation, stabilization, and acceleration for alkylation of the α-trifluoromethylated carbanions is needed for their synthetic application, as well as stabilization by the electron-withdrawing α-substituent. The reported α-substituted α-trifluoromethyl carbanions can be roughly categorized into three classes based on their structures. The first category, A, is π-conjugation-stabilized carbanions, which are stabilized by ester, nitro, sulfone, carbonyl, or phenyl groups. α-Substituents of these carbanions can delocalize the negative charges on their π-system with large σR electron-withdrawing effects; this prevents accumulation of negative charge on the fluorine atoms. The second category, B, consists of carbanions with sp3 orbitals either of highly halogenated carbanions—examples include pentafluoroethyl(trimethyl)fluorosilicate, pentafluoroethyllithium, and α,α-dichloro-β,β,β-trifluoroethylzinc species—or of cyclic structures such as oxiranyl- and aziridinyllithiums. Both of these carbanions are also stabilized since they reduce molecular orbital (MO) overlapping of the carbanion orbital to C−F bond orbitals. The third category, C, has carbanions with their anion center at the sp2 orbital, such as α-trifluoromethylated alkenyl carbanions and imidoyl carbanions. These sp2 orbitals of the carbanion center usually have a small overlap with the C−F bonds of trifluoromethyl groups. The small overlap is able to suppress the E2-type eliminations. α-Trifluoromethylated carbanions are, in general, unstable. Their stability is largely affected by factors like hybridization of the orbital that accommodates lone pair electrons, the electronic nature of the α-substituents, the degree of covalency in a bond between the carbon and metal, the class of countercation, stabilization by chelation of a metal cation, and so on. The stability, therefore, can be sometimes controlled by tuning these factors adequately so that they can be used for organic synthesis. The chemistry of α-trifluoromethylated carbanions for organic synthesis has been progressing steadily. However, the simplest trifluoroethyl and trifluoroacetyl carbanions have never been successfully produced and employed for organic synthesis. Elegant generation and synthetic application of these metal species are one of the most attractive and challenging subjects for active investigation in the future." @default.
- W2020120897 created "2016-06-24" @default.
- W2020120897 creator A5056406555 @default.
- W2020120897 creator A5061319512 @default.
- W2020120897 creator A5087452956 @default.
- W2020120897 date "2008-06-14" @default.
- W2020120897 modified "2023-09-30" @default.
- W2020120897 title "α-Trifluoromethylated Carbanion Synthons" @default.
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- W2020120897 doi "https://doi.org/10.1021/ar7002573" @default.