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Stereoselective Formation of Quaternary Stereogenic Centers via Alkylation of α‑Substituted Malonate-Imidazolidinones

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journal contribution
posted on 16.01.2015, 00:00 by Thobela Bixa, Roger Hunter, Ana Andrijevic, Wade Petersen, Hong Su, Francis Dhoro
A new stereoselective alkylation methodology is presented for formation of chiral, nonracemic quaternary centers via a chiral auxiliary protocol involving α-alkylated malonate imidazolidinones. Based on two X-ray structures of quaternized products, the diastereoselectivity observed may be rationalized via a transition-state involving an s-transC–N conformation of the C–N bond of the auxiliary, with the metal cation (K+) chelated into the malonate six-membered hole as a Z-enolate. A deprotection protocol involving ethanethiolate exchange of the imide to the corresponding thioester, followed by a standard Fukuyama reduction and a borohydride reduction, furnishes α,α′-quaternized β-hydroxypropionates in high ee overall.