Selection between the enantiotopic faces of an olefin occurs in the sterically controlled carbonylation of styrene with [Pd(phen)(p‐CH3C6H4SO3)2] as catalyst to give the title compound 1. The identification of the polymer end groups and the parallel reactions with other catalytic systems shed light on the mechanism of the reaction.
Cationic palladium complexes 2 containing coordinated phosphino(dihydrooxazo1e) ligands 1 give catalytic systems which allow the production of alternating styrene-carbon monoxide copolymers. Depending on the symmetry of the ligand, the copolymers are produced either with a highly isotactic or with an essentially completely atactic microstructure. Termination of the polymeric chain is mainly due to aa-H-elimination reaction. Both linear ((E)-PhCH=CHCO-) and branched (CH2=C(Ph)CO-) unsaturated end groups were identified.
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