Allylstannanes cross-coupling

Alkyl halides possessing / -hydrogens are usually poor substrates for carbonylative cross-coupling due to competitive / -hydride elimination/ Allyl chlorides can be used in carbonylative cross-coupling with allylstannanes/ phenyl-, 3-furyl, or vinylstannanes " to afford allylketones in modest to good yields. Divinylketones can be accessed through the reaction of vinylstannanes with vinyl iodides or vinyl triflates, with the latter requiring the addition of LiCl. Synthetic potential of this method has been proved in the formation of macrocyclic ketone jatrophone. In the reaction of vinyl triflates with tetramethyltin or aryltrimethylstannanes the additional activation by ZnCle is required. 

The 5-bromoimidazole 363 cross-coupled with an allylstannane 364 with Pd(0) as the catalyst to give allylated product 365 in good yield (Scheme 86) <2006JOC3159>. 

Sulfones. Sodium sulfinates displace aryl iodides in the presence of Cul in DMF. Cross-coupling of organostannanes. By catalysis of Cul, allylstannanes can react... 

Cross-coupling of allyl halides with allylstannane to form 1,5-hexadiene (352) is known [134]. Yamamoto has made an interesting observation that allylation of aldehydes took place to give homoallyl alcohol 353 by the reaction of allyl... 

TABLE 12. Pd-Catalyzed Cross-Coupling of Alkenylstannanes with Allylstannanes... 

Palladium(II)-catalysed cross-coupling reactions involving stan-nanes have continued to be developed, a-Halogeno-esters and -lactones couple with allylstannanes and a-stannyl-ketones in good... 

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. 

Arenesulfonyl chlorides have also been cross-coupled in the presence of Pd with both vinyl- and allylstannanes to provide the corresponding sulfones. ... 

The carbonylative cross-coupling reaction of allyl chlorides with phenyl-, 3-furyl-, and vinylstannanes is more fruitful than the reaction with allylstannanes (Scheme 14)... 

The reaction of allyl bromides with allyltin reagents, catalysed by palladium or zinc chloride, gives cross-coupled products without allylic transposition in the allyl halide partner, but with predominant allylic rearrangement from the tin partner. Similar unsymmetrical cross-couplings of allylstannanes with allyl acetates have also been observed (Scheme 19). ... 

Synthesis of Vinyl and Allyl Sulfones. In addition to the methods presented above, vinyl and allyl sulfones have been prepared by the palladium-catalyzed cross coupling of vinyl- and allylstannanes with sulfonyl chlorides (eq 30). ... 

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