Allylic compounds Tetrakis palladium

Substitution reactions of allylic nitro compounds often lead to rearranged products, as in palladium(0)-catalysed aminations and alkylations. Thus treatment of the nitro ester 419 with piperidine in the presence of tetrakis(triphenylphosphine)palladium yields a mixture of the unrearranged and rearranged amines 420 (R = piperidin-l-yl) and 421... 

Recently the use of allylic halide (see compound 96, Scheme 34) or sulfonate for the introduction of a malonyl residue at C-2 of pyranose derivatives using tetrakis(triphenyl-phosphine)palladium complex has been reported [132]. In this case, the malonyl chain is introduced anti to the leaving group at the 7-position. 

For example diacetate 240, treated with the anion of diethyl malonate, or with diethylamine, in the presence of triphenylphosphine and catalytic amounts of tetrakis(triphenylphosphine)palladium(0), gives the branched chain and amino compounds 242 and 243, respectively, both in 80% yield, via the jr-allyl Pd-complex 241 (Scheme 25 compare 145 146).230 Other... 

Kosugi, M., Sasazawa, K., Shimizu, Y., Migita, T. Reactions of allyltin compounds. III. Allylation of aromatic halides with allyltributyltin in the presence of tetrakis(triphenylphosphine)palladium ° . Chem. Lett. 1977, 301-302. 

Similar dicarborating cis-exo additions are achieved with up to 99 % yield if aryl or vinyl halides and various organotin compounds, such as vinyl-, phenyl-, ethynyl- and allyl(tributyl)tin systems, are added to norbornene in the presence of tetrakis(triphenylphosphane)palladium(0) or di-chlorobis(triphenylphosphane) as catalyst precursor7,30,80-81. Also reported are cis-exo dicarbo-rative additions to the norbornene skeleton, and their application to the synthesis of prostaglandin endoperoxide analogs, which employ stoichiometric amounts of palladium compounds16. 

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