Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

[Image: see text] Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH(2)SiMe(3))(Me(6)Tren)] (1-Na) (Me(6)Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me(6)Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH(2)SiMe(3))(Me(6)Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH(2)SiMe(3)](∞) as the CH(2) feedstock, replacing the widely used but hazardous/expensive C=O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on.