TY - JOUR T1 - Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation. AU - Davison,Nathan, AU - McMullin,Claire L, AU - Zhang,Lu, AU - Hu,Shu-Xian, AU - Waddell,Paul G, AU - Wills,Corinne, AU - Dixon,Casey, AU - Lu,Erli, Y1 - 2023/03/08/ PY - 2023/3/10/pubmed PY - 2023/3/10/medline PY - 2023/3/9/entrez SP - 6562 EP - 6576 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 145 IS - 11 N2 - 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(CH2SiMe3)(Me6Tren)] (1-Na) (Me6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH2SiMe3)(Me6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH2SiMe3]∞ as the CH2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/36890641/Li_vs_Na:_Divergent_Reaction_Patterns_between_Organolithium_and_Organosodium_Complexes_and_Ligand_Catalyzed_Ketone/Aldehyde_Methylenation_ DB - PRIME DP - Unbound Medicine ER -