Organotin vinyltins

Free-radical copolymerization of trimethyl- or tributylvinyltin with styrene or methyl methacrylate results in low ( 10%) yield of copolymer. Moreover, both the reaction rate and viscosity decrease considerably with higher vinyltin content in the starting mixture 49). These findings imply that organotin monomers tend to inhibit free-radical copolymerization. 

Organotin compounds can be effectively used as substrates in the palladium-catalyzed cross-coupling reactions of alkenyliodonium salts [66,67]. For example, the reaction of alkenyliodonium triflate 84 with 5-stannylated uracil 83 proceeds smoothly to provide cross-coupled products 87 in moderate yield. The same products 87 are obtained in almost quantitative yield in the palladium-catalyzed cross-coupling of uracil iodonium triflate 85 and vinyltin 86 (Scheme 39) [67]. 

Carbonylative coupling of vinyl triflates with organotins (12, 470-471).3 The final step in a synthesis of the macrocyclic diterpene jatrophone (2) was effected by carbonylative coupling of a vinyl triflate with vinyltin catalyzed by bis(acetonitrile)-dichloropalladium. 

The stabilizing effect of organotin compounds can also be used for internal stabilization. In this respect, a French patent of 1957 suggests copolymerization of vinyl chloride with small amounts of a vinyltin compound (e.g., the vinyldiethyl laurate of tin), which considerably improves the thermal stability over homopolymeric vinyl chloride (8). An American patent of 1959 suggests two types of organotin compounds as stabilizers (13) ... 

Franzen [56] has reviewed advances in the Suzuki, Heck, and Stille reactions in solid-state organic synthesis. There are basically two ways of adapting the Stille reaction to solid-state conditions. Either the organotin moiety or the organic residue can be attached to a solid support Nicolaou et al. [57] reported a very elegant intramolecular reaction of a polystyrene-supported vinyltin spedes bearing a terminal vinyl iodide moiety to give a 1,3-diene (Scheme 6.16) this reaction formed part of a synthesis of the natural product (S)-zearalenone. 

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