Desymmetrization of C2‐Symmetric Bis(Boronic Esters) by Zweifel Olefinations

anti‐Configured 1,3‐dimethyl deoxypropionate motifs are important sub structures in natural products. Herein, we describe a bidirectional approach for the rapid construction of natural products featuring such motifs by using C2‐symmetrical 1,3‐bis(boronic esters). As for its application in convergent syntheses it was important to establish a selective mono‐Zweifel olefination we describe the scope and limitations by using different 1,3‐bis(boronic esters) and nucleophiles. This protocol takes advantage of the combination of the Hoppe–Matteson–Zweifel chemistry, which was elegantly put into practice by Aggarwal et al. In order to show its applicability the total syntheses of two natural products, serricornin and (+)‐invictolide, were performed. It's a crab! By combining the Hoppe, Matteson, Aggarwal, and Zweifel chemistry, a bidirectional access to polyketides featuring the challenging 1,3‐deoxypropionate motif is presented. The desymmetrization of various 1,3‐bis(boronic esters) led to synthetically interesting building blocks. With this reliable method the pheromones invictolide and serricornin were synthesized.