Allylstannanes Stille reactions

Similar reactions can be carried out by using a tin(ll) compound rather than metallic tin.264-266 The allylstannanes are still easily handled but are much more reactive than the simple alkylstannanes, and their principal modes of reaction are summarized in Scheme 8. All these reactions, and particularly the carbonyl addition reactions (X=Y = R2C=0), are important in organic synthesis, and are covered in that respect in Volume 9. Only... 

As organotin compounds (organostannanes) undergo smooth Pd-catalysed transmetallation, aryl halides react with a wide variety of aryl-, alkenyl- and alkylstannanes [139]. Coupling with allylstannane is the first example [140]. The reaction is called the Migita-Kosugi-Stille or Stille coupling. Aryl, alkenyl, allyl, alkynyl and benzyl... 

In 2003, when the second edition appeared, it was clear that the Stille chemistr/ had really come of age, as shown by the increasing number of applications of palladium-catalyzed cross-coupling reactions of vinyl- and arylstannanes in natural product synthesis and in advanced organic synthesis. In the past decade, these types of applications, of course, remained very important and, in addition, the use of allylstannanes in palladium-catalyzed coupling reactions received much attention. Cross-coupling of allylstannanes with imines also forwarded the area of asymmetric catalysis. 

This methodology was further extended to allylstannanes (Grieco and Bahsas, 1987). Still in the context of Mannich-type reactions, it was shown that the rate of reaction of phenols and ketones with secondary amines in the presence of formaldehyde was greatly increased in aqueous media compared with alcoholic or hydrocarbon solvents (Tychopoulos and Tyman, 1986). More recently, Kobayashi and Ishitani (1995) reported the catalysis of the reaction of vinyl ethers with iminium salts by lanthanide triflates ... 

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