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Polyaniline coated on particles of celite is used as support to load palladium catalyst. This heterogenized Celite•PANI•Pd system, is used as an efficient catalyst for chemoselective hydrogenation reactions. The catalyst is characterized by usual spectral, analytical techniques and studied for hydrogenation reactions at ambient conditions. The mild reaction conditions allow the control over the reactions and excellent selectivity is achieved in number of conversions. Hydrogenation of a carbon–carbon double bond was favored over other polar π‐bond systems, while labile functional groups such as benzyl ether, benzyl esters, cyano, nitro and halogen remained unaffected. Primary amines were converted to N,N‐dimethyl amines with formaldehyde, the double bond of coumarin was selectively hydrogenated without opening of the lactone functionality.

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