104758-27-2Relevant articles and documents
Asymmetric Aldol Reactions. Use of the Titanium Enolate of a Chiral N-Acyloxazolidinone To Reverse Diastereofacial Selectivities
Nerz-Stormes, Maryellen,Thornton, Edward R.
, p. 2489 - 2498 (1991)
Aldol reactions of the titanium enolate of (S)-N-propionyl-4-isopropyl-2-oxazolidinone (readily derived from L-valine) with representative aldehydes give high diastereofacial selectivities for the syn aldol adducts expected from chelation control.This represents a remarkable reversal in selectivity compared with the corresponding boron enolate, thus permitting either enantiomeric form of β-hydroxy-α-methyl carboxylic acids to be made from a single, readily available oxazolidinone simply by changing the metal.A lithium interference effect is shown to be easily prevented by use of excess titanium.Use of diethyl ether as solvent rather than THF significantly enhances the stereoselectivity.Mechanistically, the observed stereochemical reversal constitutes very strong evidence that chelation is operative with titanium, presumably through a chelated chairlike transition structure.In this transition structure, the conformation would be rigidly locked by chelation and the titanium would be at least hexacoordinate, resulting in a "superaxial" ligand, thus nicely explaining the high stereocontrol.
Asymmetric Samarium-Reformatsky Reaction of Chiral α-Bromoacetyl-2-oxazolidinones with Aldehydes
Fukuzawa, Shin-Ichi,Matsuzawa, Hiroshi,Yoshimitsu, Shin-Ichi
, p. 1702 - 1706 (2007/10/03)
The samarium(II) iodide mediated asymmetric Reformatsky-type reaction of chiral 3-bromoacetyl-2-oxazolidinones with various aldehydes was studied. A series of chiral 4-substituted 2-oxazolidinones 1-3 and 5,5-disubstituted "SuperQuat" oxazolidinones 4-5 were employed as chiral auxiliaries of the α-bromoacetic acid. The reaction of 1 with various aldehydes gave the α-unbranched β-hydroxy carboximides in good yields with high diastereomeric excess values (up to >99% de). The majority of the reaction product derived from 5,5-diphenyl SuperQuat 5 were highly crystallinity; a single recrystallization yielding a diastereomerically pure product with the other diastereomer not detectable by spectroscopic methods. The absolute configurations of the β-hydroxy carboximides were determined by signs of optical rotations of the corresponding known ethyl esters referring to the literature values. Hydrolytic cleavage of the appended of β-hydroxy moieties from the auxiliary SuperQuats was readily achieved under mild conditions using lithium hydroxide; the corresponding carboxylic acids and the returned SuperQuats were obtained in good yields without any evidence of racemization. The first step of the reaction is the reduction of the α-bromo group to produce the samarium enolate, which adds to an aldehyde. The absolute configuration of the adduct (7i) derive from benzaldehyde was found to be R, with the samarium enolate favoring the transition state predicted from chelation control of the reagent; this is in analogy to the discussion that has been used for the corresponding titanium enolate. The stereochemistry of the reaction may be explained by incorporating the Nerz-Stormes-Thornton chair transition structure model.
Highly diastereoselective samarium-Reformatsky reaction of chiral α- bromoacetyl-2-oxazolidinones with aldehydes
Fukuzawa, Shin-Ichi,Tatsuzawa, Masahiro,Hirano, Kohki
, p. 6899 - 6900 (2007/10/03)
Samarium(II)iodide mediated highly diastereoselective Reformatsky type reaction of chiral α-bromoacetyl-2-oxazolidinones with aldehydes.
