Hydroformylation reaction (or oxo-process) is one of the most versatile methods for the functionalization of the double bond C-C by means of an addiction of hydrogen (H2) and carbon monoxide (CO) in order to add a formyl group (-CHO) in organic molecules. The common procedure to perform this reaction is in presence of different types of transition metals like Co, Ru, Pt, Fe and Rh, specific ligands (phosphine or phosphite spices) and a mixture 1:1 of H2 and CO (syngas). This process requires high pressure of these gasses (50-80 barr) by using special troublesome equipment like autoclaves, long reaction times (1-4 days) and hazardous organic solvents (i. e. toluene). It is here reported a fully sustainable and generally applicable protocol for the regioselective hydroformylation of terminal alkenes, using cheap commercially available catalysts and ligands, in mild reaction conditions (70 °C, 9 bar, 40 min). The process can take advantages from both micellar catalysis and microwave irradiation to obtain the linear aldehydes as the major or sole regioisomers in good to high yields. The substrate scope is largely explored as well as the application of hydroformylation in tandem with intramolecular hemiacetalization thus demonstrating the compatibility with a broad variety of functional groups. The reaction is efficient even in large scale and the catalyst and micellar water phase can be reused at least 5 times without any impact in reaction yields. The efficiency and sustainability of this protocol is strictly related to the in situ transformation of the aldehyde into the corresponding Bertagnini’s salt that precipitates in the reaction mixture avoiding organic solvent mediated purification steps to obtain the final aldehydes as pure compounds.

Micellar catalysis for sustainable hydroformylation

ACS Fall 2021

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