Palladium-catalyzed carbonylation reactions of aromatic halides in the presence of various nucleophiles have undergone rapid development since the pioneering work of Heck and co-workers in 1974, such that nowadays a plethora of palladium catalysts are available for different carbonylative transformations. The carboxylic acid derivatives, aldehydes, and ketones prepared in this way are important intermediates in the manufacture of dyes, pharmaceuticals, agrochemicals, and other industrial products. In this Review, the recent academic developments in this area and the first industrial processes are summarized.

Palladium-catalyzed carbonylation reactions of aryl halides and related compounds.

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.

Fluoride-induced 1,2-elimination of o-trimethylsilylphenyl triflate provided a convenient route to benzyne under mild conditions where detriflation from an intermediary aryl anion appeared to occur in preference to protonation even in the presence of alcohols.

Fluoride-induced 1,2-elimination of o-trimethylsilylphenyl triflate to benzyne under mild conditions

Stereochemical Control in Organic-Synthesis Using Silicon-Containing Compounds

Molecular Rearrangements of Organosilicon Compounds

The triisopropylsilyl group as a hydroxyl-protecting function

trans-.beta.-Trimethylsilylvinyllithium

Direct carbamoylation of alkenyl halides.

Treatment of allylic and benzylic halides with N,N-dimethylcarbamoyl(trimethyl)silane in the presence of tetrakis(triphenylphosphine)palladium(0) affords tertiary amides, which arise from the replacement of the halogen by the N,N-dimethylcarbamoyl group.

Robert F. Cunico

Papers

The triisopropylsilyl group as a hydroxyl-protecting function

trans-.beta.-Trimethylsilylvinyllithium

Direct carbamoylation of alkenyl halides.

Palladium-catalyzed conversion of benzylic and allylic halides into α-aryl and β,γ-unsaturated tertiary amides by the use of a carbamoylsilane

Diels--Alder reaction of .alpha.,.beta.-unsaturated trihalosilanes with cyclopentadiene