Aryl halides with vinylstannane

Palladium can also catalyze cross-coupling between aryl halides and aryl or vinylstannanes and there are examples of application of this reaction in the synthesis of pyrroles and indoles. 1-Tosyl-3-(tri-n-butylstannyl)indole gives good yields of coupling products with vinyl and aryl iodides and triflates. The recommended catalyst is tris-(dibenzylideneacetone)-dipalladium (5 mol%) used with triphenylarsine (10 mol%) (Equation (121)) <94TL2405>. 

Aryl halides (Br, I) have been converted in good yields into the corresponding arylstannanes or -silanes by treatment with RgSn2 (R = Bu, Me) or Hexamethyldisilane, respectively, in the presence of catalytic Pd(Ph3P)4 (eq 29). Aryl and vinyl triflates produce aryl- and vinylstannanes under similar conditions, provided Hexamethyldistannane and LiCl are used as co-reactants. In some cases, the presence of additional PhsP has been observed to improve yields. By using the (Ph3Sn)2Zn-TMEDA complex, vinyl halides can also be converted into vinylstannanes. ... 

Csp Csp C Bond Formation. Takeda et al. have reported that the stereospecific allylation of vinylstannanes with allylic halides proceeded in the presence of copper iodide (and in the absence of palladium) in dipolar aprotic solvents such as DMSO and THF at room temperature. The stereoselectivity of the reaction was dependent on the stractures of the vinylstannanes and allylic halides, and also on the leaving group of allylic halides employed. 0 -Aryl malonates can be synthesized by Cul-catalyzed C-C bond formation between aryl iodides (bearing a variety of functional groups) and diethyl malonate in the presence of CS2CO3 and 2-phenylphenol as the ligand (eq 25). ... 

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