Bi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation and Crotylation of Aldehydes.

IIn this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids, allowing for the formation of enantioenriched homoallylic, propargylic and crotylic alcohols (up to >99% ee, dr >20:1). These boronate substrates provided superior enantioselectivities, allowing for the reactions to proceed with low catalyst loading (0.5-5 mol%) and reduced reaction time (15 min at room temperature for aldehyde allylboration). A wide substrate scope was exhibited, and the novel boronates provided high enantiocontrol. Reactions with substituted allyl boronates and aldehydes yielded vicinal stereogenic alcohols bearing β-tertiary or quaternary carbon centers. High enantio- and diastereoselectivities were found due to the closed six-membered chair-like transition state, with backbone modifications of the boronate and its interactions with the chiral phosphoric acid being the most likely contributing factor.

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