Final Report Summary - ICSMAGC (Innovative Catalysis and Small Molecule Activation:Toward 'Green' Chemistry) The FP7–MC–CIG project No 304218 “Innovative Catalysis and Small Molecule Activation: Toward ‘Green’ Chemistry (ICSMAGC)” has focused on ‘green’ (sustainable) chemistry, which is concerned with environment, health, and safety – and thus our society in general. Catalysis is a ‘green’ key technology in the 21st century for the synthesis of complex molecules with biological and other activities.Unsurprisingly, various councils have identified catalysis as a major research area to be funded.Moreover, catalysis is an important field for industry as it has a major role in the creation of new materials and may lead to the improvement of existing processes. Further significant developments –with high impact on the field of catalysis– rely on the discovery of innovative catalysts, the invention of novel modes for catalytic activation of strong bonds, and the careful elucidation of reaction intermediates and mechanisms involved. Fundamental studies toward these goals are particularly worthwhile, because unprecedented reactivity and unique selectivity may be uncovered, ultimately leading to entirely new concepts and perspectives in chemistry. We have contributed to this endeavor with the FP7–MC–CIG project “ICSMAGC” directed toward the design and development of novel catalysts, with the aim to increase the efficiency of existing reactions, to find unprecedented reactivity and selectivity, to enable challenging bond transformations, and to invent fundamentally new reactions. The ultimate goal is to streamline organic synthesis via previously underexplored or unrecognized catalysis. Another focus of our research is the catalytic activation of strong bonds in small molecules and the development of unprecedented selective bond transformations in water or alternative ‘green’ solvents. The overall theme of the FP7–MC–CIG project “ICSMAGC” has been to explore chemical elements in their unusually low-oxidation or low-valence states because these molecules potentially display intriguing properties readily exploitable in catalysis. These features include ‘hidden’ Lewis basicity, acidity, or unique ambiphilicity, that is a switchable’ acid–base character at a single element center in view of unprecedented dual catalytic activation modes. The candidates we have examined comprise specific low-toxic metals and non-metals. This innovative concept requires critical ligand and counterion design and control for expression and exploitation in catalysis, for small molecule activation, and in ‘green’ organic media. We have successfully developed several entirely new types of catalyses involving low-oxidation state species from main groups metals [group 13: Ga(0)/(I) & Al(0)/(I)] and non-metals [group 14: C(II), C(0); group 15: N(I)]. Moreover, we have developed formal C–H bond activations of alkenes [sodium or potassium amide catalysts] and N-unprotected indoles [copper(I)/lithium carbonate species]. The involved transformations include C–C, C–Hal, and C–N bond formations: allylations and propargylations of acetals/ketals/aminals/imines; aza-Morita–Baylis–Hillman reactions; halogenations; hydrazinations; cyanations; trifluoromethylations.
