Selective and stable tetraphosphite for Rh-catalyzed linear hydroaminomethylation of aliphatic and aromatic terminal olefins

Abstract

A selective and stable tetraphosphite ligand was reported for rhodium-catalyzed linear hydroaminomethylation of aliphatic and aromatic olefins with unprecedented high TOF (up to 12,060 h-1), high chemoselectivities (up to 99.9%...

Micellar Catalysis for a Sustainable Hydroaminomethylation Process in Water

“…19−23 HAM is particularly suitable for the sustainable large-scale production of amines. 24,25 As a tandem transformation composed of an HF (the most applied catalytic process in industry), followed by an imine formation and hydrogenation, HAM needs to be carefully optimized to have good chemo-and regioselectivity (linear/branched intermediate aldehydes from HF), avoiding possible side reactions such as olefin hydrogenation and isomerization, aldol condensation, and the like. HAM is fully atom-economical, being able to incorporate all the atoms of the starting materials and gaseous reagents inside the final product with water as the sole byproduct.…”

“…Despite these reaction improvements, the purposed methodologies are still poorly atom economic and usually involve the introduction of the aromatic moiety in products obtained by HF. − In this context, hydroaminomethylation (HAM) has the potential for becoming a very ecofriendly approach to the synthesis of substituted amines, however finding only a very limited application in anilines synthesis. − HAM is particularly suitable for the sustainable large-scale production of amines. , As a tandem transformation composed of an HF (the most applied catalytic process in industry), followed by an imine formation and hydrogenation, HAM needs to be carefully optimized to have good chemo- and regioselectivity (linear/branched intermediate aldehydes from HF), avoiding possible side reactions such as olefin hydrogenation and isomerization, aldol condensation, and the like. HAM is fully atom-economical, being able to incorporate all the atoms of the starting materials and gaseous reagents inside the final product with water as the sole byproduct.…”