The use of organosodium intermediates in the synthesis of alkyltin chlorides

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

“…Organosodium complexes were first reported in 1858 by James Alfred Wanklyn, describing a reaction between ethyl iodide and sodium metal. , In the following centuries, despite discrete reports of their synthesis and structures, − as well as their applications in organic, ,− inorganic, and polymer − syntheses, organosodium chemistry is largely overshadowed by the dominating organolithium chemistry, − which was first reported in 1917, nearly 60 years later than Wanklyn’s report in 1858. The underdeveloped status of organosodium chemistry was widely attributed to the highly reactive nature and the corresponding low thermostability of these complexes .…”

Synthetic Aspects of Tetraorganotins and Organotin(IV) Halides

“…In that case, a Wurtz-type reaction of SnCl 4 with an in situ prepared organosodium can be more efficient (Eq. (1), M ¼ Na) [46][47][48][49][50]. In this way, tetrahexyltin and even tetraoctyltin can be prepared in yields up to 80%.…”

Tin

“…Octylchloride gives only a moderate yield of the required tetraalkyltin, and dodecyl chloride gives none at all. 53 Organozinc reagents have also been used to provide the carbon nucleophile. The Simmons-Smith reagent, ICH 2 ZnI, can be used for preparing iodomethyltin compounds, which can serve as precursors of further functionally substituted organotin compounds (Equation (20) Trifluoromethyltin halides (CF 3 ) n SnBr 4 _ n , n = 1, 2, or 4, can be obtained by treating SnBr 4 with bis(trifluoromethyl)mercury or cadmium.…”

“…Similarly, with AIBN initiation, 2-chloropent-4-ene gives only pentene, but at 1 . 3 GPa it gives only tributyl(5-chloropentyl)tin (Equations (53) and (54)). Hydrostannation o f an alkene or alkyne can also be catalysed by transition metals, particularly palladium.…”

“…265 Thus, tetrabutylbis(3-benzoylpropionato)distannoxane exists in a simple 4 4 4 ladder structure, 305 but a 6-4-6 ladder (52) is more common as in, for example, tetrabutylbis(trichloroacetato)distannoxane 306 or tetramethyldipivalatodistannoxane. Tetraphenylbis(trichloroacetato)distannoxane has been isolated in two different crystalline forms; in one, two carboxylate groups are bidentate, and two are monodentate, giving a 6-4-6 ladder structure, and in the other, all four carboxylate groups are bidentate to two tin atoms giving a structure consisting of four six-membered rings surrounding a four-membered ring (53) In tetramethyldiacetatodistannoxane, however, three of the acetate groups in the dimer are bidentate, bridging two tin atoms, and the fourth is bidentate to a single tin atom, with some further weak interactions (54). 308 The next stage in the hydrolysis gives the compounds HOR 2 SnOSnR 2 X.…”