Cationic Planar Chiral (η6-Arene)Mn(CO)3+ Complexes: Resolution, NMR Study in Chiral-Oriented Solvents, and Applications to the Enantioselective Synthesis of 4-Substituted Cyclohexenones and (η6-Phosphinoarene)Mn(CO)3+ Complexes

Eloi, Antoine; Rose‐Munch, Françoise; Rose, Éric; Pille, Ariane; Lesot, Philippe; Herson, Patrick

doi:10.1021/om100564v

Cited by 19 publications

(15 citation statements)

References 67 publications

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“…The distance of the crossing to the Fermi-level is in the range of 100-200 meV. Within the materials C 9 H 10 F 3 NO [29] and C 10 H 12 BrNO [30], similar crossings can be found in the conduction band. The distance of the crossing to the lowest unoccupied state is about 200 meV, as can be seen in Fig.…”

Section: Materials Data and Data Miningmentioning

confidence: 60%

“…We point out the first real material examples in the class of three-dimensional organic crystals hosting isolated Dirac nodes in the electronic structure: C 6 H 7 ClO 3 25 , C 10 H 10 Br 2 Cl 3 NO 2 26 , C 12 H 13 NO 2 27 , C 13 H 12 N 2 O 28 , C 9 H 10 F 3 NO 29 , and C 10 H 12 BrNO 30 . It will be shown that the found Dirac nodes are a consequence of the orthorhombic crystal structure of the space group P 2 1 2 1 2 1 (#19).…”

Section: Introductionmentioning

confidence: 99%

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Data Mining for Three-Dimensional Organic Dirac Materials: Focus on Space Group 19

Geilhufe

Borysov

Bouhon

et al. 2017

Sci Rep

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We combined the group theory and data mining approach within the Organic Materials Database that leads to the prediction of stable Dirac-point nodes within the electronic band structure of three-dimensional organic crystals. We find a particular space group P212121 (#19) that is conducive to the Dirac nodes formation. We prove that nodes are a consequence of the orthorhombic crystal structure. Within the electronic band structure, two different kinds of nodes can be distinguished: 8-fold degenerate Dirac nodes protected by the crystalline symmetry and 4-fold degenerate Dirac nodes protected by band topology. Mining the Organic Materials Database, we present band structure calculations and symmetry analysis for 6 previously synthesized organic materials. In all these materials, the Dirac nodes are well separated within the energy and located near the Fermi surface, which opens up a possibility for their direct experimental observation.

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Section: Materials Data and Data Miningmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Data Mining for Three-Dimensional Organic Dirac Materials: Focus on Space Group 19

Geilhufe

Borysov

Bouhon

et al. 2017

Sci Rep

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“…This approach has been also successively applied to investigate new assymmetric reactions leading to enantiopure complexes, such as chiral (η 6 -arene) chromium tricarbonyl complexes [217] (see Fig. 27a) or cationic planar chiral (η 6 -arene)Mn(CO) 3 + complexes [218].…”

Section: (A) (B)mentioning

confidence: 99%

“…Spectral discrimination using deuterium NMR in CLCs is not specific to enantiomers of organic compounds. It is also applicable to chiral organometallic compounds as exemplified by the cationic planar chiral manganese complex derivative 8 [218].…”

Section: Enantiopurity In Asymmetric Synthesis Involving Deuterated Materialsmentioning

confidence: 99%

Multinuclear NMR in polypeptide liquid crystals: Three fertile decades of methodological developments and analytical challenges

Lesot

Aroulanda

Berdagué

et al. 2020

Progress in Nuclear Magnetic Resonance Spectroscopy

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NMR spectroscopy of oriented samples makes accessible residual anisotropic intramolecular NMR interactions, such as chemical shift anisotropy (RCSA), dipolar coupling (RDC), and quadrupolar coupling (RQC), while preserving high spectral resolution. In addition, in a chiral aligned environment, enantiomers of chiral molecules or enantiopic elements of prochiral compounds adopt different average orientations on the NMR timescale, and hence produce distinct NMR spectra or signals. NMR spectroscopy in chiral aligned media is a powerful analytical tool, and notably provides unique information on (pro)chirality analysis, natural isotopic fractionation, stereochemistry, as well as molecular conformation and configuration. Significant progress has been made in this area over the three last decades, particularly using polypeptide-based chiral liquid crystals (CLCs) made of organic solutions of helically chiral polymers (as PBLG) in organic solvents. This review presents an overview of NMR in polymeric LCs. In particular, we describe the theoretical tools and the major NMR methods that have been developed and applied to study (pro)chiral molecules dissolved in such oriented solvents. We also discuss the representative applications illustrating the analytical potential of this original NMR tool. This overview article is dedicated to thirty years of original contributions to the development of NMR spectroscopy in polypeptide-based chiral liquid crystals.

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“…The ee observed after recrystallisation proved that no racemization occurred during the rearomatization step in good agreement with our initial assumption. 41 Thus, NMR in the chiral mesophase is a perfect tool for analyzing chiral charged metallic complexes.…”

Section: Rearomatizationmentioning

confidence: 99%

Planar chiral (η5-cyclohexadienyl)- and (η6-arene)-tricarbonylmanganese complexes: synthetic routes and application

Rose‐Munch

Rose

2011

Org. Biomol. Chem.

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Planar chiral arenetricarbonylchromium complexes have been intensively investigated and they have been applied as valuable building blocks for asymmetric synthesis and as ligands for asymmetric catalysis. In contrast, in the field of the isoelectronic cationic [(η(6)-arene)Mn(CO)(3)](+) complexes, until these last 10 years, very few studies were published involving nonracemic planar chiral cationic complexes and their potential applications, certainly because of the difficult access to enantiopure starting material. In 2009, however, the discovery of the first resolution of such compounds opened a new area for their application in the field of organic as well as of organometallic enantioselective syntheses. We felt it important to write a review on this subject to give an up-to-date summary of the methodologies used to prepare enantiomerically pure planar chiral neutral [(η(5)-cyclohexadienyl)Mn(CO)(3)] and cationic [(η(6)-arene)Mn(CO)(3)](+) complexes as well as their potential in enantioselective synthesis.

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Cationic Planar Chiral (η⁶-Arene)Mn(CO)₃⁺ Complexes: Resolution, NMR Study in Chiral-Oriented Solvents, and Applications to the Enantioselective Synthesis of 4-Substituted Cyclohexenones and (η⁶-Phosphinoarene)Mn(CO)₃⁺ Complexes

Cited by 19 publications

References 67 publications

Data Mining for Three-Dimensional Organic Dirac Materials: Focus on Space Group 19

Data Mining for Three-Dimensional Organic Dirac Materials: Focus on Space Group 19

Multinuclear NMR in polypeptide liquid crystals: Three fertile decades of methodological developments and analytical challenges

Planar chiral (η5-cyclohexadienyl)- and (η6-arene)-tricarbonylmanganese complexes: synthetic routes and application

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