Intermolecular Heck reaction, solid support

B.xiv.c. Intermolecular Heck Reactions on Polymeric Support. Combinatorial chemistry has initiated a reappraisal and consequent renaissance in synthesis of compounds attached to polymeric supports. Therefore, it comes as no surprise that Pd-catalyzed reactions are among the most widely explored reactions for the generation of combinatorial libraries on solid phase. The first example of the intermolecular Heck reaction on solid phase was reported in 1994. In this article, 4-vinylbenzoic acid was attached to Wang resin and coupled with aryl halides/triflates under catalysis with Pd(OAc)2 (Scheme 45). Similar... 

Intramolecular formation of large rings can be carried out efficiently on solid support, which may help to suppress competitive intermolecular reactions, as illustrated by some recent examples Macrocyclisation of the acrylamido peptide-3-iodobenzylamide 13 via Heck reaction on solid support proceeds more rapidly than the corresponding solution phase reaction22 (Scheme 1.6.5). 

In general, intermolecular Mizoroki-Heck reactions using immobilized alkenes are not as common as the variant that deals with solid-supported aryl halides, but we will come across another example in Section 14.2,3 on multicomponent Mizoroki-Heck reactions. 

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