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Dynamic Kinetic Asymmetric Cross-Benzoin Additions of β‑Stereogenic α‑Keto Esters

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journal contribution
posted on 17.12.2015, 05:23 by C. Guy Goodman, Jeffrey S. Johnson
The dynamic kinetic resolution of β-halo α-keto esters via an asymmetric cross-benzoin reaction is described. A chiral N-heterocyclic carbene catalyzes the umpolung addition of aldehydes to racemic α-keto esters. The resulting fully substituted β-halo glycolic ester products are obtained with high levels of enantio- and diastereocontrol. The high chemoselectivity observed is a result of greater electrophilicity of the α-keto ester toward the Breslow intermediate. The reaction products are shown to undergo highly diastereoselective substrate-controlled reduction to give highly functionalized stereotriads.