The Palladium-Catalyzed Carbonylative Telomerization Reaction with Phenols, Polyphenols and Kraft Lignin.

An efficient carbonylative coupling reaction of two equivalents of 1,3-butadiene, yielding aryl nona-3,8-dienoate esters, is performed with phenols as nucleophile, and promoted by palladium-based catalysts. Optimization study reveals the key role of benzoic acid as a cocatalyst. The suggested catalyst combination enables the conversion of a wide scope of variously substituted phenols into corresponding esters with a high yield. Further tests were performed with diphenols, naturally-occurring phenols and an industrial grade Kraft lignin, thus, indicating the scope of this reaction for transforming industrially relevant polyphenolic structures.

Palladium-Catalyzed Functionalization of Kraft Lignin: Ether Linkages through the Telomerization Reaction.

Kraft lignin was efficiently functionalized with octadienyl ether linkages through the palladium-catalyzed telomerization of 1,3-butadiene. Comparison with molecular model substrates assessed the grafting of phenols and alcohols and an optimization study led to up to 69 % conversion of the total number of hydroxyl groups present in lignin. This catalytic study evidenced the partial oxidation of triphenylphosphine into triphenylphosphine oxide and triphenylphosphine sulfide by contaminants present in the industrial grade kraft lignin. The telomerised lignin is a malleable material and a preliminary study of the thermal properties showed a decrease in the glass transition in comparison with the starting material.