Alkylamines are valuable as targets and intermediates for medicinal chemistry and natural product synthesis. Likewise, amino-functionalization remains attractive as a method for commodity polymer upcycling. However, the direct transformation from alkane C–H to C–N bonds remains limited and challenging. We have developed metal-free selective method for direct sp3 C-H imination with hypervalent iodine oxidants under mild reaction condition. The first imination reaction gives good yield and then the resulting ketone imines can be hydrolyzed or reduced to get primary ammonium salts or secondary amines. In contrast to the widely accepted mechanism of Löffler-Hoffman-Freytag CH amination, we proposed a unique mechanism involving iminyl radicals and hydrogen-atom transfer. We have since applied this methodology to postsynthetic polymer modification. This approach can improve the properties of commodity polymers and contribute to upcycling plastic waste, generating new, functional materials that cannot get from traditional synthetic routes.

Metal-free Selective sp3 C–H Imination and Polymer Modification

ACS Spring Meeting 2021

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