Palladium in Organic Synthesis

General Features
Palladium enjoys two stable oxidation states, the +2 state and the zerovalent state. It is the facile redox interchange between these two oxidation states which is responsible for the rich reaction chemistry that palladium complexes display. Each oxidation state has its own unique chemistry.
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Palladium(II) complexes
Palladium(II) complexes are electrophilic, and tend to react with electron-rich organic compounds, particularly olefins and arenes.

R = Ph, Me

Stable, PPh3 less labile

a catalyst precursor for Pd(0)-catalyzed processes

Palladium(0) complexes
Palladium(0) complexes are strong nucleophiles and strong bases, and most commonly are used to catalyze reactions involving organic halides, acetates and triflates. By far the most commonly used palladium(0) complex is Pd(PPh3)4, 'tetrakis' (triphenylphosphine)palladium(0).
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Pd(PPh3)4
This yellow, slightly air-sensitive (as a solid), crystalline solid is commercially available. expensive, and with four PPh3 contributing 1048 to its molecular weight, 1 g of Pd(PPh3)4 contains very little expensive palladium and much of the inexpensive phosphine. tendency to lose its catalytic activity on standing, but with no accompanying change in appearance. Better to prepare one's own material frequently and in small batches.
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 It is easy to prepare, by reducing almost any palladium(II) complex in the presence of excess phosphine.

Commonly, palladium(0)phosphine complexes are generated by reduction in situ and used without isolation, both saving time and permitting the use of phosphine ligands other than triphenylphosphine.
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Pd(dba)2, the bisdibenzylidine acetone complex.

This is prepared by simply boiling palladium(II) chloride and dba together in methanol, which acts as the reducing agent (becoming oxidized to formaldehyde). It is air stable, notwithstanding the fact that it is a palladium(0) complex.
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 Purification (rarely necessary) by recrystallization from chloroform produces crystals of Pd2(dba)3CHCl3, which has the same activity as Pd(dba)2. Perhaps the most widely used catalyst precursor for Pd(0)-catalyzed processes is Pd(OAc)2. It is very easily reduced in situ to palladium(0) by almost anything, including carbon monoxide, alcohols, tertiary amines, olefins, Main Group organometallics and even phosphines, all common ingredients in Pd(0)-catalyzed reactions.
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Pd olefin Chemistry

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 the order of complexation is CH2=CH2 > RCH=CH2 > cisRCH=CHR > trans-RCH=CHR R2C=CH2, R2C=CHR; R2C=CR2 does not complex at all. Since palladium(II) is electrophilic, electron-rich olefins such as enol ethers and enamides complex strongly whereas electron-deficient olefins complex poorly or not at all. stable olefin complexes are not only unnecessary, but actually a hindrance to catalysis. Once complexed to Pd(II), the olefin becomes generally reactive towards nucleophilic attack, this reversal of normal reactivity (electrophilic attack) being a consequence of coordination.
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 Attack usually occurs at the more substituted position of the olefin (that which would best stabilize positive charge) and from the face opposite the metal. Nucleophiles, should be poor ligands for Pd.

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Oxygen Nucleophiles
Wacker process: the formal oxidation of ethylene to acetaldehyde which involves, as the key step, palladium(II)-catalyzed nucleophilic addition of water to ethylene. little general use in organic synthesis

palladium(II)-catalyzed oxidation of terminal olefins to methyl ketones is useful.

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 since terminal olefins complex most strongly, the reaction is selective for terminal over internal olefins. Copper(I) chloride or copper(II) chlorideoxygen (1 atm) is most commonly used as the reoxidant, although a stoichiometric amount of benzoquinone provides milder conditions.

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 Require the use of tert-butyl hydroperoxide as a reoxidant, N-methylpyrrolidinone or 2propanol as solvent and Na2PdCl4 as catalyst at 50 80C. Via a different mechanism
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using stoichiometric quantities of palladium(II), since the substrates and/or products were unstable to the relatively harsh copperoxygen redox conditions

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 Carboxylic acid as nucleophile

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Palladium-catalyzed 1,4bisacetoxylation of 1,3-dienes

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An intramolecular version

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Nitrogen nucleophiles: a stronger ligand than olefins

effectively poisoning the catalyst

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