Difunctionalized compounds

Aryl- or alkenylpalladium comple.xcs can be generated in situ by the trans-metallation of the aryl- or alkenylmercury compounds 386 or 389 with Pd(Il) (see Section 6). These species react with 1,3-cydohexadiene via the formation of the TT-allylpalladium intermediate 387, which is attacked intramolecularlv by the amide or carboxylate group, and the 1,2-difunctionalization takes place to give 388 and 390[322]. Similarly, the ort/trt-thallation of benzoic acid followed by transmetallation with Pd(II) forms the arylpalladium complex, which reacts with butadiene to afford the isocoumarin 391, achieving the 1,2-difunctionalization of butadiene[323]. 

Gulea M, Masson S (2003) Recent Advances in the Chemistry of Difunctionalized Organo-Phosphorus and -Sulfur Compounds. 229 161-198 Hackmann-Schlichter N, see Krause W (2000) 210 261-308 Hadjiaraoglou LP, see de Meijere A (2000) 207 149-227... 

Recent Advances in the Chemistry of Difunctionalized Organo-Phosphorus and -Sulfur Compounds... 

Two new 3,6-difunctionalized isovoacangines were found in T. sessilifolia (174). The major compound (116, C22H26N205, amorphous, [a]D -55°) had in its mass spectrum fragments from the aliphatic portion similar to those of 115, whereas fragments from the indole moiety were shifted 30 amu. LiAlH4 reduction... 

Due to the migration of C=C bond, the conjugated esters formed can accept the attack of a second nucleophile. Thus, by applying different difunctionalized benzenes, benzo-fused five-membered heterocyclic compounds 526 can be prepared... 

Habib-Zahmani H, Hacini S, Charormet E, Rodriguez J (2002) A new multicomponent domino transformation of 1,3-dicarbonyl compounds one-pot regio-, chemo- and stereoselective access to valuable alpha,gamma-difunctionalized alpha-ketoesters and amides. Synlett 1827-1830... 

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