Asymmetric 1,3-Dipolar Cycloaddition Reactions

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.

Die organisch-chemische Synthese hat stets eine grose Faszination auf den Chemiker ausgeubt, und sie wird auch in Zukunft nichts von ihrer Bedeutung verlieren. Es ist eine Binsenweisheit, das alle Chemiker - und nicht nur die - auf die Synthese chemischer Verbindungen, mit denen sie arbeiten wollen, angewiesen sind. So ist die organisch-chemische Synthese heute mehr denn je die Schnittstelle von Organischer Chemie, Biologie. Biochemie, Medizin, Physik und Materialwissenschaft. Man sollte auch nicht vergessen, das die Grundlage der chemischen Industrie die Synthese ist. Fur den Synthetiker aus Leidenschaft aber ist die Synthese weit mehr als nur Mittel zu dem Zweck, Verbindungen in die Hand zu bekommen; sie ist Ausdruck seiner Kreativitat. Intelligenz und seines handwerklichen Konnens, aber auch seiner Ausdauer.

Sequentielle Transformationen in der Organischen Chemie eine Synthesestrategie mit Zukunft

Nucleophilic Trifluoromethylation Reactions of Organic Compounds with (Trifluoromethyl)trimethylsilane

Methods for the synthesis of gem-difluoromethylene compounds

Synthesis of perfluoro-2-alkynenitriles

Barbier-type reaction with trialkylstibine 1

An effective synthesis of 2,2-difluoro-3-hydroxy esters

A Novel Olefination of Carbonyl Compounds with α-Bromoacetic Ester Mediated by Tri-n-butylstibine.

A novel synthesis of tetrasubstituted fluoroolefins via eliminative nucleophilic addition of β-retophosphonium salts

Yanchang Shen

Papers

Synthesis of perfluoro-2-alkynenitriles

Barbier-type reaction with trialkylstibine 1

An effective synthesis of 2,2-difluoro-3-hydroxy esters

A Novel Olefination of Carbonyl Compounds with α-Bromoacetic Ester Mediated by Tri-n-butylstibine.

A novel synthesis of tetrasubstituted fluoroolefins via eliminative nucleophilic addition of β-retophosphonium salts