Intramolecular amidopalladation

A tandem cyclization of an amide bearing two olefinic moieties is shown in Scheme 14 [19],[20] Intramolecular amidopalladation followed by insertion of the resulting C—Pd bond into another olefinic moiety present in the molecule leads to a bicyclic heterocycle after /3-Pd—H elimination An analogous reaction is also given in Scheme... 

The stereochemistry of the related intramolecular amidopalladation that converts the cw-tosylamido alkenes (98) into the corresponding pyrrolidines (99) in the presence of the chiral ligand (100) has been shown to be controlled by the Pd(II) salt employed as the catalysts. Thus, with (CF3C02)2Pd, the reaction proceeds as an anft -attack of the electrophilic Pd + and the NHTs group (101) with 96% ee, whereas the less efficient syn-addition (102) is preferred by (AcO)2Pd (with mere 20% ee). The syn/anti mechanism of the ring closure was established by deuterium labelling. i... 

Intramolecular amidopalladation has also been used in the construction of isoin-dolinones (110) from hydroxamic derivatives (109). In the presence of ligand (111), the product was obtained in <99% ee. The use of MeCN as a highly coordinating solvent (ff) proved to be essential. ... 

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See also in sourсe #XX -- [ ]

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