Vinyltins reaction with

Xenon difluoride (XeF ) is the electrophilic fluorinating reagent whose reactions with vinyltin compounds have been studied most exhaustively. " A series of vinyl fluorides prepared according to this procedure is listed in Table 1. 

Table 1. Synthesis of Vinyl Fluorides by Reaction of Vinyltin Compounds with Xenon Difluoride...

Xenon difluoride is a better fluorinaling reagent for vinyltin compounds than cesium fluoroxysulfate (compare entry 1 in Tables 1 and 2). Besides this, cesium fluoroxysulfate (which can be prepared from elemental fluorine and cesium sulfate) is known to be shock sensitive and to undergo detonation upon hcaling. However, cesium fluoroxysulfate is the alternative choiee in the ease of some vinyltin compounds, such as 2- and 3-(trimethylstannyl)indolcs (Table 2, entries 5 7), whose reactions with xenon difluoride are not effective. 

Terminal difluoro- and fluoroalkenes 7 can be prepared in good yields by reaction of the corresponding fiuorovinyltin or vinyltin compounds with 1 -(chloromethyl)-4-fluoro-1,4-diazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Table 3)."... 

Table 3. Synthesis of Terminal Fluoroalkenes by Reaction of Vinyltin Compounds with F-Teda BF ...

S.8.5.6.2. by Reaction of Vinyltin Compounds with Transition- or Inner Transition-Metal-Carbonyl Complexes. 

Vinylic halides can be coupled to give 1,3-butadienes (134) by treatment with activated copper powder in a reaction analogous to the Ullmann reaction (13-11). " This reaction is stereospecific, with retention of configuration at both carbons. Vinyhc halides can also be coupled with Zn—NiCl2, " " and with -BuLi in ether in the presence of MnCl2. " The coupling reaction with vinyltin reagents and vinyl halides occurs with a palladium catalyst. " ... 

Tor a coupling reaction using a butenolide-vinyltin reagent, see Rousset, S. Abarbri, M. Thibonnet, J. Duchene, A. Parrain, J.-L. Org. Lett. 1999, 1, 701. For a vinyltin reagent with a nitrogen substituent (a tinylated enamide), see Miniere, S. Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385. 

Allylic halides couple effectively with vinyltin reagents to provide the corresponding 1,4-dienes in high yields.2 Like nickel- and palladium-catalyzed Grignard reactions with allylic ethers, this reaction also proceeds with net inversion of configuration at the allylic center. Similarly, vinyl epoxides react... 

Vinyltin derivatives react with lead tetraacetate to yield usually the alkynes, and vinyl-mercurials react with lead tetraacetate to yield the corresponding enol acetates. However, addition of mercury(II) salts to the vinyltin reactions draw the reaction towards formation of the enol acetate. The involvement of an alkylidenecarbene intermediate as an alternative decomposition pathway has been excluded. ... 

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