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Significance: The authors report copper-catalyzed asymmetric iterative and domino cross-aldol reactions. A variety of 1,3-polyols were obtained in high yields and high diastereoand enantioselectivities. Comment: In this reaction, the use of amine additives permits asymmetric triple and quadruple aldol reactions to be performed in a one-pot process. The method should be useful for the straightforward synthesis of enantiomerically and diastereomerically enriched 1,3-polyols. Bn O OBpin 1. MesCu (10 mol%) (R)-DTBM-SEGPHOS (10 mol%) i-PrOH (10 mol%)

Copper-Catalyzed Asymmetric Cross-Aldol Reactions