Gwilherm Evano studied chemistry at the Ecole Normale Supe ´rieure in Paris (France) and received his Ph.D. from Universite ´Pierre et Marie Curie in 2002 under the supervision of Franc ¸ois Couty and Claude Agami. After postdoctoral study with James S. Panek at Boston University, working on the total synthesis of the ansamycin natural products Cytotrienin A and Reblastatin, he joined the CNRS as Charge ´de Recherche at the University of Versailles in 2004. His research interests focus on asymmetric synthesis and reactivity of nitrogen heterocycles, copper-catalyzed cyclization reactions, and the total synthesis of natural products. Nicolas Blanchard obtained his Ph.D. in 2000 from Paris VI University (France) under the supervision of Professor J. Cossy and Dr. C. Meyer, working on the total synthesis of the ionophoric antibiotic zincophorin. He then joined Professor W. R. Roush (University of Michigan) for a postdoctoral stay (2001-2002) as a Lavoisier fellow, working on the total synthesis of the plecomacrolide formamicin. In late 2002, he joined the CNRS as Charge ´de Recherche in Professor Kouklovsky's laboratory (Orsay University, France). In 2006, he moved to the group of Prof. J. Eustache (Haute-Alsace University, France). His research interests focus on the synthesis of biologically relevant compounds using new methodologies including nitroso Diels-Alder cycloadditions and stereoselective metalmediated transformations.

Ynamides display an exceptionally fine balance between stability and reactivity. They also offer unique and multiple opportunities for the inclusion of nitrogen-based functionalities into organic molecules, and are emerging as especially useful and versatile building blocks for organic synthesis. Recent breakthroughs in the preparation of these substrates have revitalized interest in nitrogen-substituted alkynes, and the beginning of the 21st century has witnessed an ever-increasing number of publications reporting the development of new reactions or synthetic sequences starting from ynamides. This Review highlights major developments in this area.

A broadly applicable copper catalyst for photoredox transformations of organic halides is reported. Upon visible light irradiation in the presence of catalytic amounts of [(DPEphos)(bcp)Cu]PF and an amine, a range of unactivated aryl and alkyl halides were shown to be smoothly activated through a rare Cu(I)/Cu(I)*/Cu(0) catalytic cycle. This complex efficiently catalyzes a series of radical processes, including reductions, cyclizations, and direct arylation of arenes.

Keteniminium ions have been demonstrated to be remarkably useful and versatile reactive intermediates in chemical synthesis. These unique heterocumulenes are pivotal electrophilic species involved in a number of efficient and selective transformations. More recently, even more reactive ‘activated’ keteniminium ions bearing an additional electron-withdrawing group on the nitrogen atom have been extensively investigated. The chemistry of these unique reactive intermediates, including representative methods for their in situ generation, will be overviewed in this review article.1 Introduction2 The Chemistry of Keteniminium Ions3 The Chemistry of Activated Keteniminium Ions4 Keteniminium Ions: Pivotal Intermediates for the Synthesis of Natural and/or Biologically Relevant Molecules5 Conclusions and Perspectives

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Mild reaction conditions are the advantage of the title reaction, which allows straightforward entry to a variety of ynamides starting from readily available 1,1-dibromo-1-alkenes, which act as attractive alkynylating agents (see scheme; EWG = electron-withdrawing group, DMF = N,N-dimethylformamide).

Photocatalyzed and photosensitized chemical processes have seen growing interest recently and have become among the most active areas of chemical research, notably due to their applications in fields such as medicine, chemical synthesis, material science or environmental chemistry. Among all homogeneous catalytic systems reported to date, photoactive copper(I) complexes have been shown to be especially attractive, not only as alternative to noble metal complexes, and have been extensively studied and utilized recently. They are at the core of this review article which is divided into two main sections. The first one focuses on an exhaustive and comprehensive overview of the structural, photophysical and electrochemical properties of mononuclear copper(I) complexes, typical examples highlighting the most critical structural parameters and their impact on the properties being presented to enlighten future design of photoactive copper(I) complexes. The second section is devoted to their main areas of application (photoredox catalysis of organic reactions and polymerization, hydrogen production, photoreduction of carbon dioxide and dye-sensitized solar cells), illustrating their progression from early systems to the current state-of-the-art and showcasing how some limitations of photoactive copper(I) complexes can be overcome with their high versatility.

Inamide zeichnen sich durch ein außergewöhnlich ausgefeiltes Gleichgewicht von Stabilität und Reaktivität aus. Sie bieten eine Vielzahl von Möglichkeiten zur Einführung einer Stickstoff‐Funktionalität in organische Moleküle und werden zunehmend als besonders nützliche und vielseitige Bausteine für die organische Synthese angesehen. Aktuelle Durchbrüche bei der Herstellung von Inamiden haben das Interesse an der Chemie von Stickstoff‐substituierten Alkinen wiederbelebt, und seit Anfang des 21. Jahrhunderts ist eine stetig wachsende Zahl an Publikationen zur Entwicklung neuer Reaktionen oder Sequenzen ausgehend von Inamiden zu verzeichnen. Dieser Aufsatz wird die wesentlichen Entwicklungen in diesem Bereich erörtern.