Stille-type reaction

The synthesis of fully conjugated semiconducting para-phenylene ladder polymers by microwave-assisted palladium-mediated double Suzuki and Stille-type reactions has been demonstrated by Scherf and coworkers (Scheme 6.27) [58], The procedure, which yields polymeric material in ca. 10 min, has no adverse effects on the quality of the polymers and displays a high degree of reproducibility. Compared... 

Stille-type reactions can be performed under analogous conditions. For example, reactions of aryllead triacetates with arylboronic acids give rise to the respective biaryls in yields of around 75%.46... 

An efficient aqueous phase Suzuki-Miyaura reaction of activated aryl chlorides with aryl boronic acids has been reported. The method uses a new D-glucosamine-based dicyclohexylarylphosphine ligand for the palladium catalyst and works well with nitro-and cyano-activated chlorides.32 The aryl fluoride bond has been considered inert to palladium-catalysed substitution reactions. However, a computational study, backed up by experiment, shows that the presence of a carboxylate group ortho to fluorine will allow reaction both with phenylboronic acids in a Suzuki-type reaction and with organotin reagents in a Stille-type reaction the presence of the adjacent oxyanion stabilizes the transition state.33... 

Intramolecular Reaction of Aryl and Vinyl Halides Heck-, Suzuki-, and Stille-Type Reactions... 

Efficient construction of the macrocyclic ring is essential for achievement of the total synthesis of macrolide antibiotics. Macrolactonization and intramolecular Wittig-type reaction have been frequently used so far. In recent years, olefin metathesis and Stille-type reaction for formation of C-C bonds have been efficiently applied to the construction of macrocyclic rings. 

Most of the catalytic cross-coupling reactions are based on the activation of a G-F bond of monofluorinated aromatic substrates. The Kumada-Gorriu-, Suzuki-, and Stille-type reactions are catalyzed by nickel or palladium complexes. 

Tin Derivatives. 5-Alkynylpyridines can be prepared by a Stille-type reaction between a l-bromoalkyne and a 5-trimethylstannylpyridine 163 (Scheme 68). ... 

Another intriguing cascade of an intramolecular Heck-type reaction followed by an intermolecular Stille coupling produces the dienyne 98 starting from the enyne 96 and the stannane 97 [322] (Scheme 8.25). The reversed sequence of a Stille-type reaction followed by a Heck reaction has also been applied. It is also possible to terminate such a sequence after transmetallation from a zincate [180a,c], either added to the reaction mixture [180a] or generated in situ from an iodoalkene [180c]. 

The transmetallation of oxidative addition products of alkenyl halides and zerovalent palladium species by organotin reagents is an important step in Stille type reactions and its mechanism depends on many variables. A recent review on this topic accounts for transmetallation of alkenylpalladium(ii) species.The involvement of 14-electron T-shaped species [PdX(R)(L)] in Stille reactions involving alkenyl and other substrates has been refuted as unrealistic. Instead, associative ligand substitution at palladium is advocated, which has been corroborated by full and quantitative evaluation of kinetic data as well as MO considerations. ... 

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