During the last decades, the employment of both transition-metal-based catalysts and highly polar organometallic compounds (e.g., organolithium or Grignard reagents) by a myriad of research groups worldwide has granted access to a plethora of diverse organic scaffolds with highly complex structures via formation of new carbon-carbon or carbon-heteroatom bonds either in their stoichiometric or catalytic version. In the pursuit of formation of the above bonds, the following objectives have been traditionally challenging in the chemistry of s-block elements:

i) the regio- and stereoselectivity of the process;
ii) the tolerance of different functional groups; and
iii) the final yield of the reaction.

The field of Green Chemistry has emerged over the past twenty years to become nowadays a major force in how a chemical process can be made sustainable. This change in thinking in chemical synthesis is the result of ecological challenges and societal pressure. However, the ever more limited availability of natural resources demands non-trivial solutions in the manufacture of pharmaceutical products, chemical commodities, and new materials.
In this context, there is an increasing interest in the scientific community toward the development/selection of cheap and environmentally friendly reaction media, as 80–90% of the total mass balance of many chemical processes is composed of solvents, thereby creating a heavy environmental impact. Moreover, the physico-chemical properties of a given solvent are known to strongly influence the yield and the selectivity of the desired reaction. Thus, the possibility of tuning solvent properties in order to make product isolation easier, along with effective catalyst recycling, are of the utmost importance.
In the quest for the “ideal” and universal green reaction medium for any reaction, the following non-conventional solvents have stood out in recent years from all others in the field of metal-catalyzed and metal-mediated organic transformations:

i) water;
ii) ionic liquids;
iii) supercritical fluids;
iv) perfluorinated solvents;
v) biomass-based solvents (e.g., 2-methyl-THF, lactic acid, γ-valerolactone, glycerol); and
vi) Deep Eutectic Solvents (DESs).

This Research Topic will collect the best selection of state-of-the-art contributions in the fields of metal-catalyzed reactions and/or main-group-mediated organic transformations run in any of the aforementioned non-conventional solvents.

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Frontiers in Chemistry

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