Crystallisation of C2-symmetric endo,endo-bicyclo[3.3.1]nonane-2-6-diols: supramolecular synthons and concomitant degrees of enantiomer separation

Nguyen, Vi T.; Chan, Isa Y. H.; Bishop, Roger; Craig, Donald C.; Scudder, Marcia L.

doi:10.1039/b900463g

Cited by 12 publications

(9 citation statements)

References 58 publications

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“…Within this list are C2 symmetrical pyrimidine (OBIPAR [76] ), phosphine (LUSZOO [77] ) and imidazole (ROJPOW [78] ) ligands, an atropsiomeric quinoline (TUWFAT [79] ), an α-methylpyridine (DOBWUN [80] ), and a chiral salen ligand (TUNMOF [81] ). Potential types of organocatalysts such as the C2 symmetrical diol (NULZEA [82] ), a PTC (phase transfer catalyst) crown ether (NOCNIC [83] ), and chiral phosphoric acid (CUVGAB [84] ), chiral ureas (RIPBUN, [85] AZUDAB [86] ), benzotetramisole (YAMBAS [87] ), amino-alcohol (HARFEN [88] ), and imidazole (PURJUJ [89] ) may also find use in asymmetric synthesis. These are only selected examples, and we would encourage the community to view our full list of structures they may deem useful to their research.…”

Section: Resultsmentioning

confidence: 99%

A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

Walsh

Barclay

Begg

et al. 2022

Preprint

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Conglomerate crystallisation is the behaviour responsible for spontaneous resolution and the discovery of molecular chirality by Pasteur. The phenomenon of conglomerate crystallisation of chiral organic molecules has been left largely undocumented and offers synthetic chemists a potential new chiral pool not reliant on biological systems to supply stereochemical information. While other crystallographic behaviours can be interrogated by automated searching, conglomerate crystallisations are not identified within the Cambridge Structural Database (CSD) and are therefore not accessible by conventional means. By conducting a manual search of the CSD, a list of over 1,700 chiral species capable of conglomerate crystallisation was curated by inspection of the synthetic routes described in each publication. The majority of these are produced by synthetic chemists who seldom note and rarely exploit the implications this phenomenon can have on the enantioenrichment of their crystalline materials. We propose that this list represents a limitless chiral pool which will continually grow in size as more conglomerate crystals are synthesised and recorded.

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Section: Resultsmentioning

confidence: 99%

A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

Walsh

Barclay

Begg

et al. 2022

Preprint

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“…In the crystallization of racemic compounds (mixtures for R and S enantiomers or racemate), three possible outcomes are possible according to Figure . The most frequent is the formation of racemic crystals where both enantiomers are intimately mixed (A).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Crystallographic Studies of Disubstituted Carboranyl Alcohol Derivatives: Prevailing Chiral Recognition?

Salvo

Paterakis

Tsang

et al. 2013

Crystal Growth & Design

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The syntheses of new o-carboranyldiols bearing aromatic rings bis-[R(hydroxy)methyl]-1,2-dicarba-closo-dodecaborane (R = 2-pyridyl 1a, 3-pyridyl 1b, 4pyridyl 1c, 2-quinolyl 1d, 4-quinolyl 1e, phenyl 1f) are reported. The compounds are obtained as mixtures of meso (syn) and racemic (anti) stereoisomers with a slight diastereomeric excess (syn:anti ratio of 0.7:1) in all cases but in 1b. The crystal structures of the meso compounds syn-1a•2MeOH, syn-1b, syn-1f•0.25H 2 O and racemic anti-1a•MeOH, anti-1a•EtOH, and anti-1d•2H 2 O are reported. We provide an analysis of these compounds by means of NMR and X-ray crystallography, in the context of crystal engineering and chiral recognition. The results show that the crystal packings for these alcohols are dominated by the supramolecular O−H•••N and/or O− H•••O hydrogen bonds. Supramolecular analysis of all compounds in this work reveals that homochiral self-assembly, that is, formation of homochiral hydrogen bonded complexes, prevails over heterochiral self-assembly (formation of heterochiral hydrogen bonded complexes).

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“…In contrast to IIIB, this complex consists of two types of chiral helical columns with opposite chirality; one is composed of (R)-1 and 5, and the other of (S)-1 and 5. [7] Complex IV is formed by the assembly of columns with opposing chirality by two types of intercolumnar interactions (Figure 4 c and 4d): a CH-p interaction between the n-butyl group in 5 and the benzene ring in (R)-1 (or (S)-1, C-p = 3.90 , as indicated by arrow A in Figure 4 c), and the benzene-benzene edge-to-face interaction between benzene rings of 5 (C-p = 3.50 , as indicated by arrow B in Figure 4 c). [6] From the X-ray crystallographic analysis, it appeared that this high degree of enantiomer separation in the racemic crystal occurs in two steps.…”

Section: Resultsmentioning

confidence: 99%

Preparation of a Spontaneously Resolved Chiral Fluorescent System Containing 4‐(2‐Arylethynyl)benzoic Acid

et al. 2013

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A spontaneously resolved chiral fluorescent system was prepared from achiral 4‐(2‐arylethynyl)benzoic acid and racemic (rac)‐1‐phenylethylamine. Although functional chiral organic materials are usually prepared from chiral molecules, the chiral organic fluorophore described herein is successfully generated from achiral and racemic molecules to form a system that emits circularly polarized luminescence (CPL) in the solid state.

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Crystallisation of C2-symmetric endo,endo-bicyclo[3.3.1]nonane-2-6-diols: supramolecular synthons and concomitant degrees of enantiomer separation

Cited by 12 publications

References 58 publications

A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

Synthesis and Crystallographic Studies of Disubstituted Carboranyl Alcohol Derivatives: Prevailing Chiral Recognition?

Preparation of a Spontaneously Resolved Chiral Fluorescent System Containing 4‐(2‐Arylethynyl)benzoic Acid

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