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For the sake of clarity, in this article, the stereochemistry of the molecules (starting materials and products) will be referred to as cis/trans; whilst for the organopalladium intermediates (π-allyl complexes) the syn/anti nomenclature will be employed.
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The nature of the ligand bound to the incoming zero-valent palladium was also found to affect the oxidative addition in a critical way, see ref.16b.
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The nature of the ligand bound to the incoming zero-valent palladium was also found to affect the oxidative addition in a critical way, see ref.16b.
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The cis/trans ratio of isomerization was found to be time dependent: 2.3:1 (30min); 1:1.3 (1hour) 1:2 (2h). After prolonged heating, the isomerization was biased by the formation of a by-product (the corresponding conjugate diene, product of elimination).
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Since the substrate is cis-configured, the use of a stabilized carbanion in palladium catalysis should lead only to the enantioenriched product of similar relative stereochemistry (retention).
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Since the substrate is cis-configured, the use of a stabilized carbanion in palladium catalysis should lead only to the enantioenriched product of similar relative stereochemistry (retention).
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A mechanism involving a ligand-dependant syn oxidative addition seems to be very difficult to rationalize in such a complex system, although it cannot be excluded.
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A mechanism involving a ligand-dependant syn oxidative addition seems to be very difficult to rationalize in such a complex system, although it cannot be excluded.
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