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A convergent synthesis of highly substituted and stereodefined skipped polyenes is described from the reductive cross-coupling of substituted 1,5-diene-3-ols with alkynes. The control of site selectivity in functionalization of the substituted diene is a central feature of this complex fragment union reaction.

Chemoselective Reductive Cross-Coupling of 1,5-Diene-3-ols with Alkynes: A Facile Entry to Stereodefined Skipped Trienes