Stannanes palladium-catalyzed coupling with alkenyl

In contrast, the Stille reaction was one of the first cross-coupling reactions performed on solid support. For the palladium-catalyzed coupling of various aryl, vinyl, or alkynyl stannanes with aryl or alkenyl bromides, iodides, or triflates, the reaction conditions employed were chosen in analogy to the liquid phase procedures and often feature an arsine or trifurylphosphine as an added ligand. Due to the tedious separation of tin and organo tin reagents or by-products in solution phase, this carbon-carbon bondforming reaction is particularly suitable for solid-phase synthesis. ... 

Palladium-catalyzed cross coupling of resin bound iodopyridine with a boronic acid (Suzuki reaction) (12) or with an alkenyl-, alkynyl-, or arylstannane (Stille reaction) (13) was effected by treatment of resin 5 with 4 equivalents of the boronic acid or stannane, 8 equivalents of K2CO3 (Suzuki reaction only), and catalytic Pd(PPh3)4 in DMF at 50 C for 20 hours. (14) Best results were achieved by running each reaction twice, with an intermediate wash of the resin, in order to drive the reaction to conq>letion. The corresponding Pd-catalyzed amination (Buchwald reaction) (15) worked well in protocol development but the reaction failed with the 3 amines attenpted during actual library preparation. 

Palladium-catalyzed cross-coupling of alkenyl stannanes with pinanediol bro-momethyl boronate (143) has been reported to give homologous allylic boronates... 

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