Gold Catalyzed Cycloisomerization Reactions Through Activation Of Alkynes

Antoine Simonneau's thesis highlights the development of new cycloisomerization reactions through the activation of alkynes with gold complexes. First Simonneau describes 1,6-enynes and their direct conversion into allenes through 1,5-hydride or ester migration processes. The author and his team used appropriate propargylic functional groups to achieve this conversion. This study shows that O-tethered 1,6-enynes carrying a strained cycloalkane at the propargylic position could undergo a cyclopropanation/ring expansion cascade reaction. The author employed this rearrangement as the starting point in the design of a new macro cycle synthesis. The next part of the thesis focuses on the cycloisomerization of diynes involving as the first step of the process the rearrangement of one alkyne partner into an allene thanks to a gold-catalyzed 1,3-shift of a propargylic ester. The thesis discloses a new cycloisomerization pattern featuring a 1,5-carbonyl transfer, giving rise to unprecedented cross-conjugated diketones. In the final part of the research, Simmoneau investigates the gold-catalyzed cycloisomerization mechanism of 1,6-enynes and questions the intermediacy of gold acetylides. By the means of NMR and mass spectrometry analysis, theoretical treatment and solution experiments, it was possible to rule out the involvement of these species in the catalytic cycle. This thesis has led to a number of publications in high-impact journals.

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students.

B. R. Buckley and H. Heaney: Mechanistic Investigations of Copper(I)- Catalyzed Alkyne–Azide Cycloaddition Reactions.- J. D. Crowley and D. A. McMorran: “Click-Triazole” Coordination Chemistry: Exploiting 1,4-Disubstituted-1,2,3-Triazoles as Ligands.- S. Lee and A. H. Flood: Binding Anions in Rigid and Reconfigurable Triazole Receptors.- M. Watkinson: Click Triazoles as Chemosensors.- H.-F. Chow, C.-M. Lo and Y. Chen: Triazole-Based Polymer Gels.- T. Zheng, S. H. Rouhanifard, A. S. Jalloh, P. Wu: Click Triazoles for Bioconjugation.- S. Mignani, Y. Zhou, T. Lecourt and L. Micouin: Recent Developments in the Synthesis 1,4,5-Trisubstituted Triazoles.

Ana Escribano Cuesta's thesis presents a detailed study of the inter- and intramolecular reactions of carbonyl compounds with 1,6-enynes using gold (I) complexes. An important part of the work involved streamlining the variables that allow the selective synthesis of different products such as tricyclic compounds, dihydropyrans, 1,3-dienes or cyclobutenes. The second chapter highlights the importance and difficulties in synthesising a cyclobutene subunit and the author includes a detailed description of how the products were prepared. The final chapter outlines the synthesis of lundurines using methodology developed by the author's research group for intramolecular gold-catalyzed cyclization of indoles with alkynes. The lundurine products developed in this work show significant in vitro cytoxicity toward B16 melanoma cells. The work in this thesis has led to a number of publications in high-profile chemistry journals.

Research on designing new catalytic systems has been one of the most important fields in modern organic chemistry. One reason for this is the predominant contribution of catalysis to the concepts of atom economy and green chemistry in the 21st century. Gold, considered catalytically inactive for a long time, is now a fascinating partner of modern chemistry, as scientists such as Bond, Teles, Haruta, Hutchings, Ito and Hayashi opened new perspectives for the whole synthetic chemist community. This book presents the major advances in homogeneous catalysis, emphasizing the methodologies that create carbon–carbon and carbon–heteroatom bonds, the applications that create diversity and synthesize natural products, and the recent advances and challenges in asymmetric catalysis and computational research. It provides readers with in-depth information about homogeneous gold-catalyzed reactions and presents several explanations for the scientific design of a catalyst. Readers will be able to understand the entire gold area and find solutions to problems in catalysis. Gold Catalysis — An Homogeneous Approach is part of the Catalytic Science Series and features prominent authors who are experts in their respective fields. Contents:From Gold in Nature to Gold Catalysts (Søren Kramer and Fabien Gagosz)Homogeneous Gold-Catalyzed Oxidation and Reduction Reactions (Liming Zhang)Gold-Catalyzed Addition of Carbon Nucleophiles to C–C Multiple Bonds, Carbonyls, and other Electrophiles (Bryon L Simmons and Hong C Shen)Gold-Catalyzed Addition of Heteroatom Nucleophile to C–C Multiple Bond (Naoki Asao, Naoya Hatakeyama and Yoshinori Yamamoto)Gold-Catalyzed Synthesis of Heterocycles (Antonio Arcadi)Gold-Catalyzed Multi-Component Reactions (Rachid Skouta and Chao-Jun Li)Gold Catalysis on Tandem and Cascade Reactions (Rai-Shung Liu)Cycloisomerization Reactions of 1, N-Enynes (Núria Huguet and Antonio M Echavarren)Gold-Catalyzed Reactions of Propargylic Esters (Louis Fensterbank, Jean-Philippe Goddard, Max Malacria and Antoine Simonneau)Gold-Catalyzed Cross-Coupling Reactions (Suzanne A Blum)Gold-Catalyzed Reactions: A Computational Approach (Elena Soriano and José Marco-Contelles)Recent Developments in Asymmetric Catalysis (Patrick Y Toullec, Alexandre Pradal and Véronique Michelet)Gold Catalysis in Natural Product Synthesis (Michael R Gesinski and F Dean Toste) Readership: Graduate students and researchers in organic chemistry. Key Features:First book on homogeneous gold catalysisProminent authorsFrom catalysts design to target-oriented applicationsA fascinating partner for modern chemistryKeywords:Gold;Catalysis;Heterocycles;Tandem;Cascade ReactionsReviews: “Gold Catalysis gives an excellent overview of a rapidly growing field. All of the thirteen chapters are written by the best practitioners. This book is certainly a “must” for laboratories working with coinage metals, but also for any organometallic group.” Guy Bertrand Distinguished Professor, University of California, San Diego Director of the UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555)

The series Topics in Heterocyclic Chemistry presents critical reviews on present and future trends in the research of heterocyclic compounds. Overall the scope is to cover topics dealing with all areas within heterocyclic chemistry, both experimental and theoretical, of interest to the general heterocyclic chemistry community. The series consists of topic related volumes edited by renowned editors with contributions of experts in the field. All chapters from Topics in Heterocyclic Chemistry are published Online First with an individual DOI. In references, Topics in Heterocyclic Chemistry is abbreviated as Top Heterocycl Chem and cited as a journal