Enantioselective organocatalytic syntheses of α-selenated α- and β-amino acid derivatives.

Selenium-containing amino acids are valuable targets but methods for the stereoselective α-selenation of simple amino acid precursors are rare. We herein report the enantioselective electrophilic α-selenation of azlactones (masked α-amino acid derivatives) and isoxazolidin-5-ones (masked β-amino acids) using Cinchona alkaloids as easily accessible organocatalysts. A variety of differently substituted derivatives was accessed with reasonable levels of enantioselectivities and further studies concerning the stability and suitability of these compounds for further manipulations have been carried out as well.

Enantioselective Bifunctional Ammonium Salt-Catalyzed Syntheses of 3-CFS-, 3-RS-, and 3-F-Substituted Isoindolinones.

We herein report the ammonium salt-catalyzed synthesis of chiral 3,3-disubstituted isoindolinones bearing a heteroatom functionality in the 3-position. A broad variety of differently substituted CFS- and RS-derivatives were obtained with often high enantioselectivities when using Maruoka's bifunctional chiral ammonium salt catalyst. In addition, a first proof-of-concept for the racemic synthesis of the analogous F-containing products was obtained as well, giving access to one of the rare examples of a fairly stable α-F-α-amino acid derivative.

Enantiospecific deoxyfluorination of cyclic α-OH-β-ketoesters.

We herein report the deoxyfluorination of cyclic α-hydroxy-β-ketoesters using diethylaminosulfur trifluoride (DAST). The reaction proceeds with excellent levels of stereospecificity, giving the configurationally inverted α-fluoro-β-ketoesters in high yields under operationally simple conditions.

Ammonium Salt-Catalyzed Ring-Opening of Aryl-Aziridines with β-Keto Esters.

We herein report an ammonium salt-catalyzed protocol for the regioselective ring opening of aryl-aziridines with β-keto esters. The reaction gives access to a variety of highly functionalized target molecules with two consecutive stereo-genic centers and can be rendered enantioselective (up to = 91:9) by using bifunctional chiral ammonium salt catalysts.