Abstract: | Stereodefined cyclohexene and cyclopentene derivatives were prepared by the coupling of allylic alcohols and other allylic precursors with unsaturated aldehydes. These reactions are based on a multicatalytic one‐pot approach involving palladium pincer complex‐catalyzed boronation, allylation and ring‐closing metathesis reactions. This reaction sequence can be performed in an operationally simple procedure affording the cycloalkene products in high overall yields and excellent regio‐ and stereoselectivities. The presented procedure has a broad synthetic scope and high functional group tolerance, which allows the synthesis of bicyclic lactone and spirane skeletons and various substitution patterns including hydroxy, silyl, vinyl, allyl, and sulfonyl groups. The studied catalytic one‐pot reactions involve up to three individual processes performed by up to four acid‐ and transition metal‐catalyzed events. |