Editing the stereochemical elements in an iridium catalyst for enantioselective allylic amination
- 5 April 2004
- journal article
- research article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences
- Vol. 101 (16) , 5830-5833
- https://doi.org/10.1073/pnas.0307967101
Abstract
Individual diastereomeric phosphoramidites and mixtures of diastereomeric phosphoramidites were evaluated in the iridium-catalyzed amination of allylic carbonates. The original process was conducted with a phosphoramidite ligand containing a resolved 2,2-dihydroxy-1,1-binaphthyl (BINOL) group and a diastereomerically and enantiomerically pure bis(phenethyl)amino group. Evaluation of the structure of the active catalyst and relative rates for reactions in the presence of catalysts containing diastereomeric ligands led to the identification of a phosphoramidite that provided the amination product with enantiomeric excess similar to the original, more structurally and stereochemically complex ligand and that contains a racemic BINOLate and an N-benzylphenethylamino group on phosphorus.Keywords
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