Introduced to the Market in the Last Decade (2001−2011) Jiang Wang,† María Sańchez-Rosello,́‡,§ Jose ́ Luis Aceña, Carlos del Pozo,‡ Alexander E. Sorochinsky, Santos Fustero,*,‡,§ Vadim A. Soloshonok,* and Hong Liu*,† †Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203, China ‡Department of Organic Chemistry, Faculty of Pharmacy, University of Valencia, Av. Vicente Andreś Estelleś, 46100 Burjassot, Valencia, Spain Laboratorio de Molećulas Orgańicas, Centro de Investigacioń Príncipe Felipe, C/ Eduardo Primo Yuf́era 3, 46012 Valencia, Spain Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel Lardizab́al 3, 20018 San Sebastian, Spain IKERBASQUE, Basque Foundation for Science, Alameda Urquijo, 36-5 Plaza Bizkaia, 48011 Bilbao, Spain Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Murmanska Street 1, 02660 Kyiv-94, Ukraine

Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011).

Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo- and transition-metal catalysis. The most challenging transformation remains the formation of the parent C-F bond, primarily as a consequence of the high hydration energy of fluoride, strong metal-fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost-efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Introduction of Fluorine and Fluorine-Containing Functional Groups

Iron Catalysis in Organic Synthesis

Electrophilic Trifluoromethylation by Use of Hypervalent Iodine Reagents

Dialkylbiaryl phosphines are a valuable class of ligand for Pd-catalyzed amination reactions and have been applied in a range of contexts. This perspective attempts to aid the reader in the selection of the best choice of reaction conditions and ligand of this class for the most commonly encountered and practically important substrate combinations.

Dialkylbiaryl phosphines in Pd-catalyzed amination: a user's guide

Being mono-aza analogues of sulfoxides and sulfones, sulfimides and sulfoximines, respectively, are important compounds in asymmetric synthesis, crop protection and medicinal chemistry. For their preparation various methods have been developed. In the search for the optimal synthetic approach for a given target compound, several parameters have to be considered which also include safety issues and availability of starting materials. In this tutorial review, we present an overview of sulfur imidation methods, classified by imidating agents and compounds with a related behaviour. The aim of this survey is to provide a practical “tool box” for the synthetic chemist by mapping the advantages and disadvantages associated with the use of these compounds.

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Sulfur imidations: access to sulfimides and sulfoximines

1,4,2-Dioxazol-5-ones are five-membered heterocycles known to decarboxylate under thermal or photochemical conditions, thus yielding N-acyl nitrenes. Described herein is a light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2-dioxazol-5-ones at room temperature, thus providing direct access to N-acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one-pot sulfur imidation/oxidation sequence catalyzed by a single ruthenium complex is reported.

Light‐Induced Ruthenium‐Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N‐Acyl Sulfimides and Sulfoximines

The interest in fluorinated sulfoximines has rapidly increased over the past twenty years. As sulfoximines are analogues of sulfones where one of the two SO units has been replaced by an SN moiety, they can confer new reactivities and properties never observed for the respective sulfones. In this tutorial review, we present the specific properties of fluorinated sulfoximines (including important bioactivities) and describe the syntheses and the applications of fluoromethyl transfer agents such as Johnson's reagent. Furthermore, we highlight the exceptional electronic effects induced by the presence of strongly electron-withdrawing fluoro-bearing sulfonimidoyl moieties, which allowed the development of remarkable super-acidifiers and super-acceptors with relevance in materials sciences.

Fluorinated sulfoximines: syntheses, properties and applications.

All domains of chemistry are increasingly impacted by organofluorine molecules, often favorably. In asymmetric synthesis of fluorinated compounds, significant achievements are the result of extensive research efforts toward appropriate experimental conditions rather than of the rationalization of fluorine effects. Most of the time, the influence of fluorine is inspected retrospectively. When elaborating a synthetic plan, the question should not be only when and how to introduce fluorine but also how to use the effects of fluorine for a desirable result. The subtle effects of fluorine atom(s) on the course of asymmetric reactions are outlined in this tutorial review. We present some selected examples of asymmetric reactions that involve fluorinated components either as reactants, catalysts, solvents or additives, and a comparative study of the stereochemical outcomes with reactions carried out in the presence of non-fluorinated analogues.

Vincent Bizet

Papers

Sulfur imidations: access to sulfimides and sulfoximines

Light‐Induced Ruthenium‐Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N‐Acyl Sulfimides and Sulfoximines

Fluorinated sulfoximines: syntheses, properties and applications.

The influence of fluorine in asymmetric catalysis

Synthesis of α-CF3-substituted carbonyl compounds with relative and absolute stereocontrol using electrophilic CF3-transfer reagents.