Industrial reaction improved: The first monocarbenepalladium(0)–olefin complex has been isolated and characterized (see structure; Pd orange, N green, S yellow, O blue). The complex exhibited unprecedented high catalyst productivity and selectivity for industrially important telomerization reactions (the dimerization of 1,3‐dienes in the presence of a nucleophile, in this case an alcohol).

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The synthesis of octadienyl-substituted alcohols via palladiumcatalyzed telomerization is described. 2-N-Methylaminoethanol, ethylene glycol, and 1,2-propylenediol react smoothly with 1,3-butadiene to give valuable intermediates for speciality polymers in high selectivity and quantitative yield on multi-100 g-scale.