Combined computational and experimental investigations on the diastereoselective hydrogenation of steroids by chiral oxazaborolidine

Göndös, György; Pálinkó, István

doi:10.1002/qua.1328

Cited by 2 publications

(1 citation statement)

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“…Theoretical computations on oxazaborolidine-catalyzed reduction of ketones have been reported by several authors. Most of the theoretical work has been carried out by Nevalainen. − Other contributions are due to Jones and Liotta, Bach et al, Linney et al, Quallich et al, Bringmann et al, , Göndös and Pálinkó, and Li et al. − A thorough survey of all these previous investigations has been recently reported by Alagona et al in this journal, and therefore we shall not comment on them in detail here (though some essential points are discussed below). In the work of Alagona et al, the authors have carried out ab initio density functional and semiempirical calculations for the system acetophenone + CBS catalyst + BH 3 .…”

Section: Introductionmentioning

confidence: 99%

A Model for Double Asymmetric Induction in the Stereocontrolled Reduction of Glycosyl α-Ketoesters with Oxazaborolidines

Harb¹,

Mf²,

Coutrot³

et al. 2004

J. Am. Chem. Soc.

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Experimental diastereoselectivities for the stereocontrolled reduction of glycosyl alpha-ketoesters into the corresponding alpha-hydroxyesters have recently been reported with unexpected results. The process is catalyzed by a chiral oxazaborolidine derivative (the so-called CBS catalyst) and represents the key step in the synthesis of glycosyl alpha-amino acids synthons, a class of compounds that allow preparation of natural glycopeptides analogues exhibiting potential therapeutic relevance. Good to very good diastereomeric excesses have been obtained for a series of reactions with different glucidic derivatives, but surprisingly, the major product obtained does not correspond to that predicted by using Corey's model. In the present work, we carry out a theoretical investigation of these reactions at the density functional level. Separated effects from the catalyst and from the glucidic derivative have been computed to rationalize the observed diastereoselectivities and the double asymmetric induction.

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