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Both syn- and anti-β-amino alcohols are common structural motifs in natural products, drug molecules, chiral ligands and catalysts. However, the currently available methods for synthesizing these motifs are limited to generate only one diastereoisomer. Therefore, development of a unified method for stereoselective access to complementary diastereomers would be highly desirable. Herein, we report a method for dual-metal-catalyzed diastereodivergent coupling of alkoxyallenes with aldimine esters. By carefully selecting the two metals and app