Hexamethyldistannane

Description

It has been generally used as raw materials for producing other compounds in organic synthesis. For example, it can react with 1,3-dienes highly regioand stereo-selectively in the presence of a catalytic amount of bis(dibenzylideneacetone)palladium to afford dimerization-double-stannation adducts in high yields.¹ The synthesis of allytrimethylstannanes with high yields was demonstrated by reaction of hexamethyldistanne with a broad range of allylic compounds including allyl acetates and allyl halides in the presence of palladium complexes.² By using this product, the direct stannylation of halopyridines and bipyridines can be accomplished by Pd catalysis.³ Besides, the addition of hexamethyldistannane to 1-alkynes was shown to yield the (Z)-1,2-Bis(Trimethylstannyl)-1-Alkenes in the presence of Pd complex.⁴

Reference

1. Tsuji, Y.; Kakehi, T., PALLADIUM-CATALYZED DIMERIZATION DOUBLE STANNATION OF 1,3-DIENES USING HEXAMETHYLDISTANNANE. J. Chem. Soc.-Chem. Commun. 1992, 1000-1001.
2. Bumagin, N. A.; Kasatkin, A. N.; Beletskaya, I. P., REACTIONS OF HEXAMETHYLDISTANNANE WITH ALLYL ACETATES AND ALLYL HALIDES CATALYZED BY PALLADIUM COMPLEXES. Bulletin of the Academy of Sciences of the Ussr Division of Chemical Science 1984, 33, 588-594.
3. Benaglia, M.; Toyota, S.; Woods, C. R.; Siegel, J. S., Synthesis of pyridylstannanes from halopyridines and hexamethyldistannane with catalytic palladium. Tetrahedron Lett. 1997, 38, 4737-4740.
4. Mitchell, T. N.; Amamria, A.; Killing, H.; Rutschow, D., SYNTHESIS OF (Z)-1,2-BIS(TRIMETHYLSTANNYL)-1-ALKENES BY PLATINUM-CATALYZED ADDITION OF HEXAMETHYLDISTANNANE TO 1-ALKYNES. J. Organomet. Chem. 1983, 241, C45-C47.
   [5] H. YOSHIDA. ChemInform Abstract: Copper-Catalyzed α-Selective Hydrostannylation of Alkynes for the Synthesis of Branched Alkenylstannanes.[J]. ChemInform, 2015, 46 44. DOI:10.1002/chin.201544208.
   [6] BO CHEN . Palladium-catalyzed carbonylative synthesis of acylstannanes from aryl iodides and hexamethyldistannane[J]. Journal of Organometallic Chemistry, 2020, 923: Article 121351. DOI:10.1016/j.jorganchem.2020.121351.
   

Chemical Properties

Clear colorless liquid

Uses

It is used to prepare aryl tin compounds for microwave-assisted Stille cross-coupling with halo pyridines or copper-mediated O-arylation of phenols.

Uses

Agricultural chemical.

Hazard

A poison by ingestion.

Chemical Reactivity

Hexamethyldistannane is a good chemical reagent that can react with unsaturated alkanes (alkynes or alkenes) and aryl iodides to form organostannanes. For example, the reaction of alkynes with hexamethyldistannane produces branched trimethylstannyl olefins^[5]. Using Pd(PPh3)4 as a catalyst and toluene as a solvent, aryl iodides and hexamethyldistannane are carbonylated to form acylstannanes at 60 °C and 10 bar CO for 16 hours. For easy separation and analysis, the resulting acylstannanes can be converted to the corresponding benzoic acids by simply stirring in air for 5 hours^[6].

Purification Methods

Wash it with H2O and extract with *C6H6, dry by filtering through powdered Na2SO4, remove *C6H6 on a rotary evaporator and fractionally distil the oily residue under vacuum (b 85-88o/45mm). It boils at ca 182o at atmospheric pressure, but it cannot be distilled in air because the hot vapours flash in the condenser. [Kraus & Session J Am Chem Soc 47 2361 1925, Morris & Selwood J Am Chem Soc 63 2509 1941, Pedley et al. Trans Faraday Soc 53 1612 1957, Beilstein 4 IV 4346.]