Rhodium-Catalyzed Parallel Kinetic Resolution of Racemic Internal Allenes Towards Enantiopure Allylic 1,3-Diketones

Lukas J Hilpert; Bernhard Breit

doi:10.1002/anie.201903365

Rhodium-Catalyzed Parallel Kinetic Resolution of Racemic Internal Allenes Towards Enantiopure Allylic 1,3-Diketones

Angew Chem Int Ed Engl. 2019 Jul 15;58(29):9939-9943. doi: 10.1002/anie.201903365. Epub 2019 Jun 6.

Authors

Lukas J Hilpert¹, Bernhard Breit¹

Affiliation

¹ Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstraße 21, 79104, Freiburg im Breisgau, Germany.

PMID: 31106496
DOI: 10.1002/anie.201903365

Abstract

A rare case of a parallel kinetic resolution of racemic 1,3-disubstituted allenes by means of a rhodium-catalyzed addition to 1,3-diketones furnishing enantiopure allylic 1,3-diketones is described. Mechanistic experiments demonstrate that the different allene enantiomers react in parallel to either the diastereomeric E- or Z-allylic 1,3-diketones with the same absolute configuration of the newly formed stereogenic center. A broad substrate scope demonstrates the synthetic utility of this new method.

Keywords: 1,3-diketones; allenes; asymmetric catalysis; parallel kinetic resolution; rhodium.