Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 19, Pages 6306-6310Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201901175
Keywords
asymmetric catalysis; ligand design; self-recognition; stereodynamics; supramolecular chemistry
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Funding
- European Research Council (ERC) [258740]
- Max-Planck-Society
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The design of a new class of fluxional biphenyl bisphosphinite (BIBIPHOS) ligands decorated with amino acid-based diamide interaction sites is reported that undergo spontaneous desymmetrization. Hydrogenation of prochiral alkenes using Rh-BIBIPHOS results in enantiomeric ratios of up to 96:4 (R/S). This stereoconvergent behavior of the fluxional BIBIPHOS ligand is triggered by pronounced intermolecular interlocking of the recognition sites, leading to the formation of a supramolecular assembly, where the axial orientation of the biphenyl ligand backbone is governed by the chirality of the amino acid moieties. Stereoinduction during catalysis is decoupled from this process and occurs as an immediate consequence of the emergent behavior of the ligands. This supramolecular system is very robust and has the potential to be adopted for other ligand designs in enantioselective catalysis.
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