Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation
Nathan Davison, Claire L. McMullin, Lu Zhang, Shu‐Xian Hu, Paul G. Waddell, Corinne Wills, Casey Dixon, Erli Lu
Abstract
High Resolution Image Download MS PowerPoint Slide 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.