Synthesis; Catalysis; Hypervalent Iodine; Alkynes; Azides
Li Yifan, Hari Durga Prasad, Vita Maria Victoria, Waser Jerome (2016), Cyclic Hypervalent Iodine Reagents for Atom-Transfer Reactions: Beyond Trifluoromethylation, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, 55(14), 4436-4454.
Vita Maria Victoria, Waser Jerome (2015), Cyclic Hypervalent Iodine Reagents and Iron Catalysts: The Winning Team for Late-Stage C-H Azidation, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
, 54(18), 5290-5292.
Vita Maria Victoria, Caramenti Paola, Waser Jerome (2015), Enantioselective Synthesis of Homoallylic Azides and Nitriles via Palladium-Catalyzed Decarboxylative Allylation, in ORGANIC LETTERS
, 17(23), 5832-5835.
Vita Maria Victoria, Miéville Pascal, Waser Jerome (2014), Enantioselective Synthesis of Polycyclic Carbocycles via an Alkynylation–Allylation–Cyclization Strategy, in Organic Letters
, 16(21), 5768.
Vita Maria Victoria, Waser Jérôme (2013), Azidation of Beta-Keto Esters and Silyl Enol Ethers with a Benziodoxole Reagent, in Organic Letters
, 15, 3246-3249.
Fernandez Gonzalez Davinia, Brand Jonathan P., Mondière Régis, Waser Jérôme (2013), Ethynylbenziodoxolones (EBX) as Reagents for the Ethynylation of Stabilized Enolates, in Advanced Synthesis & Catalysis
, 355, 1631-1639.
Gonzalez Davinia Fernandez, Benfatti Fides, Waser Jerome (2012), Asymmetric Organocatalysis Meets Hypervalent Iodine Chemistry for the alpha-Functionalization of Carbonyl Compounds, in CHEMCATCHEM
, 4(7), 955-958.
Fernández González Davinia, De Simone Filippo, Brand Jonathan, Nicolai Stefano, Waser Jerome (2011), Cyclopropane and Hypervalent Iodine Reagents: High Energy Compounds for Applications in Synthesis and Catalysis, in Chimia
, 65, 649-651.
During the last century, synthetic organic chemistry has reached a high level of sophistication. The design of molecules can now been done on the molecular level, and synthetic organic compounds have become increasingly important for the study of biological systems, the cure of illnesses and the discovery of new organic materials. With the development of these applications and the understanding gained in them, the efficient synthesis of complex molecules has become even more important. Despite the great success of the last decades, organic chemistry is still a very time-consuming and expensive process. These difficulties limit applications to simple molecules that are easier to access, but probably not optimal for their intended task. In this context, it is absolutely essential to develop new synthetic tools to increase the flexibility and efficiency of organic synthesis.In the last three years, our research has focused mostly on the discovery of new reactions for the synthesis of acetylenes. The choice of this research topic was motivated by the importance of alkynes, not only in synthesis, but also in biochemistry and materials science. Nevertheless, acetylene transfer reactions usually involve the reaction of acetylides with electrophiles, which limits the number of structures accessible. The discovery in our group of the exceptional properties of ethynyl benziodoxolones (EBX) as electrophilic acetylene synthons (Umpolung of the normal reactivity) allowed the development of new reactions, such as the ethynylation of linear keto, nitro and cyano esters, the oxyalkynylation of olefins and the direct alkynylation of heterocycles.Although very useful building blocks were accessed, the obtained products were racemic. The synthesis of enantiopure compounds is of primordial importance for their bioactivity. The main goal of this proposal renewal is the development of asymmetric alkynylation methods of enolates, based on the following approaches:-Asymmetric phase-transfer, dual activation or enamine catalysis.-The use of other asymmetric methods starting from racemic alkynylation products.The use of the obtained enantiopure products for the synthesis of important building blocks, such as bicyclic carbo- and heterocycles, non-natural amino acids and electrophilic allenes will then be studied. These compounds are important in medicinal and biological chemistry, but the incorporation of chiral quaternary centers in their structure constitutes an important challenge, that cannot be met by classical acetylide chemistry.In parallel to this research project, our studies on the alkynylation of olefins and C-H bonds will also continues, as well as the design and synthesis of new hypervalent iodine reagents for the transfer of other functional groups, in particular azides. The availability of more efficient methods for the Umpolung of acetylenes and azides will increase their utility, not only in organic synthesis, but also for applications in biochemistry and materials science.