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Abstract Double‐allylation reagents allow for the construction of highly complex molecules in an expedient fashion. We have developed an efficient, modular, and enantioselective approach towards accessing novel variants of these reagents through Cu/Pd‐catalyzed alkenylboration of alkenylboron derivatives. Importantly, we demonstrate novel use of an allylBdan reagent directly in a stereocontrolled allylation without initial deprotection to the boronic ester. These allylation products are employed in a second intermolecular allylation to access complex diol motifs, which has yet to be shown with these types of double‐allylation reagents. Overall, the modularity of this approach and the ease in which complex structural motifs can be accessed in a rapid manner signify the importance and utility of this method.more » « less
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