Fluorine has received great attention in all fields of science. “Small atom with a big ego” was the title of the Symposium at the ACS meeting in San Francisco in 2000, where a number of the current scientific and industrial aspects of fluorine chemistry made possible by the small size and high electronegativity of the atom were discussed. This small atom has provided mankind with significant benefits in special products such as poly(tetrafluroethylene) (PTFE), freon, fluoro-liquid crystals, optical fiber, pharmaceutical and agrochemical compounds, and so on, all of which have their own unique properties that are otherwise difficult to obtain.1 For instance, at present, up to 30% of agrochemicals and 10% of pharmaceuticals currently used contain fluorine atoms. Therefore, organic fluorine compounds have received a great deal of interest and attention from the scientists involved in diverse fields of science and technology. Now, not only C-F bond formation but also selective C-F bond activation have become current subjects of active investigation from the viewpoint of effective synthesis of fluoroorganic compounds. The former is highlighted by designing a sophisticated fluorinating reagent for regioand stereocontrolled fluorination and developing versatile multifunctional and easily prepared building blocks. C-F bond formation has been treated extensively in several reviews2 and books.3 The latter is a subject that has been less explored but would be promising for selective defluorination of aliphatic fluorides, cross-coupling with aryl fluorides, and * To whom correspondence should be addressed. Phone: 81-78-803-5799. Fax: 81-78-803-5799. E-mail: amii@kobe-u.ac.jp and uneyamak@cc.okayamau.ac.jp. † Kobe University. ‡ Okayama University. Chem. Rev. 2009, 109, 2119–2183 2119

C-F bond activation in organic synthesis.

1,1-Dihalo-1-alkenes are valuable synthetic tools in organic
chemistry and serve as interesting synthetic intermediates in a variety of non-metal-assisted chemical transformations. Moreover, the vinyl dihalide functionality is an attractive and versatile bidentate electrophile for organometallic chemistry.

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

Acylsilanes are a fascinating class of compounds that display a number of distinctive chemical and physical properties. The unique reactivity pattern of the acylsilane functional group [R–C(O)Si] makes them an increasingly attractive moiety in modern organic synthesis, and as such, they have been utilised in a diverse range of transformations. This review provides an overview of the recent advances in the synthesis and application of acylsilanes in organic chemistry, with a particular focus on the progress made in the last two decades.

Acylsilanes: valuable organosilicon reagents in organic synthesis

Olefin metathesis reactions with fluorinated substrates, catalysts, and solvents.

β,β-Difluorinated amino acid derivatives were synthesized via Mg(0)-promoted defluorination of α-trifluoromethyl iminoester. Bromination of the difluoroenamine afforded the bromodifluoromethyl iminoester in good yield. Pd-catalyzed asymmetric hydrogenation of the bromodifluoromethyl iminoester and the subsequent transformations provided optically active β,β-difluoroglutamic acid and β,β-difluoroproline derivatives.

Catalytic Route to the Synthesis of Optically Active β,β-Difluoroglutamic Acid and β,β-Difluoroproline Derivatives

Concise Syntheses of γ-Oxo-β,β-difluorinated Amino Acids via Chelated [3,3]-Rearrangement of Difluoroallylic Alcohols

Readily available γ,γ-difluorinated allylic alcohols obtained from trifluoroethanol were esterified efficiently. Exposure to strong base (LDA) afforded the ester enolates, in which chelation both controlled configuration and stabilised against fragmentation, which were trapped as their silyl ketene acetals. Rearrangement occurred to afford base-sensitive acid products. Esterification under mild conditions afforded the purifiable methyl esters in which the masked ketone had been released. Educts with either a benzyloxy or an allyloxy group at the α-position could be deprotected releasing the alcohols.

/pdf/synthesis-of-a-hydroxy-b-b-difluoro-g-ketoesters-via-3-3-21rrhh1c3f.pdf

Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements

Rearrangement routes to selectively fluorinated compounds

Chelated 3,3-rearrangements of difluoroallylic alcohols

Fluoroallylic alcohols are easy to synthesise by a variety of routes using one or two carbon fluorinated building blocks. Sigmatropic rearrangement then transforms these intermediates into species in which the fluorine atom (or atoms) is borne on an sp3-hybridised carbon. Alternatively, allylic alcohols can be transformed into fluorinated vinyl ether derivatives; rearrangement then affords products in which the fluorine atoms occupy a different and complementary location with respect to a carbonyl function.

Rearrangement Routes to Selectively Fluorinated Compounds

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