Palladium/BaSO

Hydrogenation catalysts Dichlorotris(triphenylphosphine)ruthenium. Iridium. Iridium tetrachloride-Triethyl phosphite. Iridium-BaSO, or CaC04. Lithium aluminum hydride. Nickel catalyst, Raney. Palladium hydroxide. Platinum catalysts. Potassium hydride. Trihydridobis(triphenyIphosphine)iridium (III). 

It is very well documented that the carbon-carbon triple bonds (e.g., alkynes) on catalytic hydrogenation gives the completely reduced product, viz. alkanes. Alkynes can also be reduced partially to give z-alkenes by palladium-calcium carbonate catalyst which has been deactivated (partially poisoned) by the addition of lead acetate (Lindlar catalyst) or Pd-BaSO deactivated by quinoline. The lead treatment poisoned the palladium catalyst, rendering it less active and the reaction is more selective. Some examples are given (Scheme 98). 

On the other hand, the racemization of amines is more difficult compared to that of alcohols. Several metal systems based on palladium (Pd), Ru, nickel (Ni), cobalt (Co), and Ir have been employed as the racemization catalysts. Pd-based catalysts include Pd/C, Pd/BaSO, and Pd/A10(0H). They are readily available but require higher temperatures for satisfactory racemization. So they should be coupled with thermostable enzymes such as Novozym 435 for the successful DKR. A possible mechanism for the Pd-catalyzed racemization of amine is described in Scheme 5.5. The racemization occurs via reversible dehydrogenation/hydrogena-tion steps including an imine intermediate. The imine intermediate can react with starting material to afford a secondary amine as the byproduct. The deamination of substrate and byproduct are also possible at elevated temperature. In case the... 

Alkynes may be reduced stereospecifically to cfs-alkenes in the presence of the Lindlar catalyst, or the related system Pd/BaSO /pyridine (Figure 23.20). More active palladium catalysts can... 

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