PMID: 11325271Apr 28, 2001Paper

Lithiated 4-isopropyl-3-(methylthiomethyl)-5,5-diphenyloxazolidin-2-one: a chiral formyl anion equivalent for enantioselective preparations of 1,2-diols, 2-amino alcohols, 2-hydroxy esters, and 4-hydroxy-2-alkenoates

The Journal of Organic Chemistry
C GaulD Seebach

Abstract

The heterocyclic compound specified in the title (and readily prepared from commercial precursors) has a sterically protected C==O group, so that direct lithiation by BuLi at the exocyclic CH(2) group is possible (3 --> Li-3). The lithiated N,S-acetal derivative (Li-3) adds diastereoselectively to aldehydes (Table 2), unsymmetrical ketones (Table 3), chalcone (1,4-addition, Scheme 2), and N-phosphinoyl- and N-sulfonylimines (Table 4). Protection of the newly formed OH groups (Scheme 3) and/or MeS/OH displacement by Hg(O(2)CCF(3))(2) in aqueous THF/acetonitrile converts the N,S-acetals into hemiaminals (--> 20) which, in turn, are readily cleaved to aldehydes, with recovery of the chiral auxiliary (1, Scheme 4). The aldehydes (especially those lacking alpha-carbonyl hydrogens) may be isolated, or they are trapped in situ by reduction to (selectively protected) diols or amino alcohols, by addition of Grignard or Li reagents, which provides diols with two stereogenic centers, by oxidation to give 2-hydroxy esters, or by olefination to provide 4-hydroxy-2-alkenoates (Scheme 5). The scope and limitations of the new, overall enantioselective transformation are determined, and the readily recovered chiral auxiliary used is compared wi...Continue Reading

Citations

Dec 1, 2006·Chemical Communications : Chem Comm·Alessandro Degl'InnocentiAntonella Capperucci
Feb 2, 2010·Chemical & Pharmaceutical Bulletin·Tito AkindeleKiyoshi Tomioka
Dec 15, 2015·Organic Letters·Zilei XiaWeiqing Xie
Jul 21, 2006·Organic & Biomolecular Chemistry·Steven D BullJames E Thomson
Jan 12, 2019·Organic & Biomolecular Chemistry·Stephen G DaviesJames E Thomson
Mar 25, 2006·Organic & Biomolecular Chemistry·Mark S ScottDarren J Dixon
Jul 7, 2020·Chemical Communications : Chem Comm·Esteban MatadorJosé M Lassaletta
Jan 24, 2017·European Journal of Organic Chemistry·Stephen M GeddisDavid R Spring
Dec 20, 2014·Organic Letters·Shuichi NakamuraHideki Masuda
Apr 20, 2014·Organic Letters·Xuliang LiuBaoguo Zhao
Aug 17, 2021·The Journal of Organic Chemistry·Jing-Ya ZhouYong-Ming Zhu
Jul 2, 2005·The Journal of Organic Chemistry·Dwight D KimPeter Beak

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