The use of water as a donor for hydrogen suitable for the reduction of several important classes of organic compounds is described. It is found that the reductive water splitting can be promoted by several metalloids among which silicon shows the best efficiency. The developed methodologies were applied for the reduction of nitro compounds, N‐oxides, sulfoxides, alkenes, alkynes, hydrodehalogenation ...

A caesium fluoride-mediated hydrocarboxylation of olefins is disclosed that does not rely on precious transition metal catalysts and ligands. The reaction occurs at atmospheric pressures of CO₂ in the presence of 9-BBN as a stoichiometric reductant. Stilbenes, β-substituted styrenes and allenes could be carboxylated in good yields. The developed methodology can be used for preparation of ...

The asymmetric Rh‐catalyzed hydrocarboxylation of α,β‐unsaturated carbonyl compounds was originally developed by Mikami and co‐workers but gives only moderate enantiomeric excesses. In order to understand the factors controlling the enantioselectivity and to propose novel ligands for this reaction, we have used computational and experimental methods to study the Rh‐catalyzed hydrocarboxylation with ...

A formal C−H carboxylation of unactivated arenes using CO₂ in green solvents is described. The present strategy combines a sterically controlled Ir‐catalyzed C−H borylation followed by a Cu‐catalyzed carboxylation of the in situ generated organoboronates. The reaction is highly regioselective for the C−H carboxylation of 1,3‐disubstituted and 1,2,3‐trisubstituted benzenes, 1,2‐ or ...

Development of safe, renewable, cheap and versatile solvents is a longstanding challenge in chemistry. We show here that vegetable oils and related systems can become prominent solvents for organic synthesis. Suzuki–Miyaura, Hiyama, Stille, Sonogashira and Heck cross-couplings proceed with quantitative yields in a range of vegetable oils, fish oil, butter and waxes used as solvents. Appropriate ...

Solvents constitute the largest component for many chemical processes and substitution of nonrenewable solvents is a longstanding goal for green chemistry. Here, we show that Pd-catalyzed carbonylative couplings, such as carbonylative cross-couplings, aminocarbonylations, and alkoxycarbonylations, can be successfully realized using renewable solvents. The present research covers not only well-established ...