Development of Sterically Hindered and Basic Sodium Amides for Catalytic Hydrogen Isotope Exchange

Abstract

AbstractSodium amides are gaining momentum in synthetic chemistry, emerging not only as more sustainable alternatives to lithium amides but also as superior reagents in synthesis and catalysis. Despite recent advances in sodium organometallics, the information available about the constitution of these reagents is very limited. Advancing the understanding on structure/reactivity correlations in sodium amide chemistry, here, we report the synthesis and characterisation of four new sodium amides, with different sterically demanding substituents (adamantyl/trimethylsilyl and dicyclohexyl groups at the nitrogen atom) and different polyamine donors as well as investigate their ability to promote catalytic hydrogen isotope exchange using deuterated benzene as deuterium source. These studies have revealed that sodium dicyclohexylamide in combination with PMDETA (N,N,N’,N’’,N’’‐pentamethyldiethylentriamine) offers only slightly lower deuterium incorporation for non‐activated arenes than sodium 2,2,6,6‐tetramethylpiperidide, which is significantly more expensive and less available.