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Iridium-Catalyzed Allylation of Chiral β‑Stereogenic Alcohols: Bypassing Discrete Formation of Epimerizable Aldehydes

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journal contribution
posted on 21.12.2012, 00:00 by Daniel C. Schmitt, Anne-Marie R. Dechert-Schmitt, Michael J. Krische
The cyclometalated π-allyliridium 3,4-dinitro-C,O-benzoate complex modified by (R)- or (S)-Cl,MeO-BIPHEP promotes the transfer hydrogenative coupling of allyl acetate to β-stereogenic alcohols with good to excellent levels of catalyst-directed diastereoselectivity to furnish homoallylic alcohols. Remote electronic effects of the C,O-benzoate of the catalyst play a critical role in suppressing epimerization of the transient α-stereogenic aldehyde.