A Valine-Derived Lithiated 3-Methylthiomethyl-1,3-oxazolidin-2-one for Enantioselective Nucleophilic Hydroxymethylation, Formylation, and Alkoxycarbonylation of Aldehydes
- 3 May 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 2 (11) , 1501-1504
- https://doi.org/10.1021/ol0000410
Abstract
The 3-methylthiomethyl-4-isopropyl-5,5-diphenyl-1,3-oxazolidin-2-one (I, prepared in three steps from Boc-valine ester) is lithiated and added to aldehydes, with protecting in situ trapping of the primary adducts, to give the N,S-acetal derivatives II of 2-hydroxy aldehydes in high yields and diastereoselectivities. Cleavage (with ready recovery of the oxazolidinone auxiliary) is possible, to afford, for instance, enantiopure 1,2-diols, selectively protected (OBn, OMOM, OTBS) in the 2-position.Keywords
This publication has 17 references indexed in Scilit:
- Stereoselective Synthesis of Trifluoromethylated Compounds: Nucleophilic Addition of Formaldehyde N,N-Dialkylhydrazones to Trifluoromethyl KetonesThe Journal of Organic Chemistry, 1999
- Asymmetric alkylations using SuperQuat auxiliaries—an investigation into the synthesis and stability of enolates derived from 5,5-disubstituted oxazolidin-2-onesJournal of the Chemical Society, Perkin Transactions 1, 1999
- A Useful Modification of theEvans Auxiliary: 4-Isopropyl-5,5-diphenyloxazolidin-2-oneHelvetica Chimica Acta, 1998
- Formation and reaction of 2-metalated N-Boc-4,4-dimethyl-1,3-oxazolidines in the presence of (−)-sparteine: new chiral formyl anion equivalentsTetrahedron: Asymmetry, 1998
- Formaldehyde SAMP-Hydrazone - a neutral chiral formyl anion and cyanide equivalentAdvanced Synthesis & Catalysis, 1998
- Highly diastereoselective reactions of ytterbium-mediated alkynyllithium and alkynylmagnesium reagents with chiral 2-acyl-1,3-oxathianes: reversal of diastereoselectivityJournal of the American Chemical Society, 1990
- Asymmetric syntheses based on 1,3-oxathianes. 2. Synthesis of chiral tertiary .alpha.-hydroxy aldehydes, .alpha.-hydroxy acids, glycols [R1R2C(OH)CH2OH], and carbinols [R1R2C(OH)Me] in high enantiomeric purity.Journal of the American Chemical Society, 1984
- Asymmetric syntheses based on 1,3-oxathianes. 1. Scope of the reactionJournal of the American Chemical Society, 1984
- Asymmetric reactions based on 1,3-oxathianes3̄Tetrahedron, 1984
- Methods of Reactivity UmpolungAngewandte Chemie International Edition in English, 1979