2018
DOI: 10.1002/chir.23007
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Supramolecular chirality transfer in a stereodynamic catalysts

Abstract: We present rhodium catalysts that contain stereodynamic axially chiral biphenol-derived phosphinite ligands modified with non-stereoselective amides for non-covalent interactions. A chirality transfer was achieved with (R)- or (S)-acetylphenylalanine methyl amide, and the interaction mechanism was investigated by NMR measurements. These interactions at the non-stereoselective interaction sites and the formation of supramolecular complexes result in an enrichment of either the (R )- or (S ) enantiomer of the tr… Show more

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Cited by 15 publications
(15 citation statements)
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“…Initial interaction studies were to be conducted on stereodynamic bisphosphinite ligands, as their rhodium complexes have a rotational barrier above 80 kJ mol −1 which allows for a distinct differentiation of the two axial isomers by NMR spectroscopy, while equilibration of the ligand still occurs at ambient temperature . Furthermore, the direct relationship between rotamer distribution and enantioselectivity in asymmetric hydrogenation reactions is known .…”
Section: Resultsmentioning
confidence: 99%
See 2 more Smart Citations
“…Initial interaction studies were to be conducted on stereodynamic bisphosphinite ligands, as their rhodium complexes have a rotational barrier above 80 kJ mol −1 which allows for a distinct differentiation of the two axial isomers by NMR spectroscopy, while equilibration of the ligand still occurs at ambient temperature . Furthermore, the direct relationship between rotamer distribution and enantioselectivity in asymmetric hydrogenation reactions is known .…”
Section: Resultsmentioning
confidence: 99%
“…Initial interaction studies were to be conducted on stereodynamic bisphosphinite ligands, as their rhodium complexes have a rotational barrier above 80 kJ mol −1 which allows for a distinct differentiation of the two axial isomers by NMR spectroscopy, while equilibration of the ligand still occurs at ambient temperature. 33 Furthermore, the direct relationship between rotamer distribution and enantioselectivity in asymmetric hydrogenation reactions is known. 42 Ligand synthesis was achieved by initial oxidative coupling of methyl vanillate 1, protection of the resulting 2,2′-biphenol with allyl bromide and saponification of the methyl ester groups of 2 to yield dicarboxylic acid 3 (see Figure 2).…”
Section: Interaction Studiesmentioning
confidence: 99%
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“…18,29 Small chiral molecules, whose racemates where known to separate well on these chiral stationary phases (CSPs), could be used to exert influence over the rotamer distribution of the ligand 2 to generate enantioselective catalysts for an asymmetric hydrogenation reaction (see Figure 3b). 30 Furthermore, various systems were developed in which enantioselective formation of transient adducts could successfully be used for the screening of enantiomeric ratios of interacting analytes. 31 Furthermore a ligand design based on the well-investigated interaction pattern between the Whelk-O selector 32 and profene-or naproxene-type molecules was explored.…”
Section: Account Synlettmentioning
confidence: 99%
“…However, this would be an exceptionally rare case. In recent years, we have developed catalysts decorated with chiral recognition units to recognize and transfer the chirality of the reaction product generated in the catalysis to the stereodynamic unit of the catalyst (Maier and Trapp, 2014;, 2017, 2018Storch et al, , 2016aScholtes and Trapp, 2019a,b,c,d). This induces a shift in the equilibrium of the stereodynamic catalyst by the recognized chirality (cf.…”
Section: Introductionmentioning
confidence: 99%