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Diastereoselective Conjugate Addition to Chiral α,β-Unsaturated Carbonyl Systems in Aqueous Media: An Enantioselective Entry to α- and γ-Hydroxy Acids and α-Amino Acids

✍ Scribed by Rosa M. Suárez; José Pérez Sestelo; Luis A. Sarandeses


Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
213 KB
Volume
9
Category
Article
ISSN
0947-6539

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✦ Synopsis


The stereoselectivity of the ultrasonically induced zinc--copper conjugate addition of iodides to chiral alpha,beta-unsaturated carbonyl systems under aqueous conditions was studied. Alkyl iodides add diastereoselectively to methylenedioxolanone 1 and methyleneoxazolidinone 2 to afford the 1,4-addition products in good yields (38-95 %) and with high diastereomeric excess (44-90 % de). The 1,4-addition to chiral gamma,delta-dioxolanyl-alpha,beta-unsaturated esters 3-5 also proceeds with good yields (51-99 %). The diastereoselectivity is dependent on the geometry of the olefin: the Z isomer 3 gives high diastereoselectivity, while the reactions with the E isomer 4 are nonstereoselective. The reaction proceeds with excellent chemoselectivity and allows the use of iodides bearing ester, hydroxy, and amino groups. Since the 1,4-addition products can be readily hydrolyzed, this methodology constitutes a novel entry for the enantioselective synthesis of alpha- and gamma-hydroxy acids and alpha-amino acids in aqueous media. The results obtained support the radical mechanism proposed by Luche, and represent one of the few examples of a radical stereoselective conjugate addition in aqueous medium.


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✍ Claudio Palomo; Raquel Pazos; Mikel Oiarbide; Jesús M. García 📂 Article 📅 2006 🏛 John Wiley and Sons 🌐 English ⚖ 85 KB 👁 1 views

## Abstract No base is required for the Mg(II)‐catalyzed conjugate addition of nitromethane to α′‐hydroxy enones in the presence of molecular sieves. Good enantioselectivities are attained using 3 or 4 Å MS and about 10 mol % of Mg(OTf)~2~‐chiral bisoxazoline complexes. Elaboration of the adducts t