Enantiodifferentiation of chiral cationic cages using trapped achiral BF4? anions as chirotopic probes

Frantz, Richard; Grange, Christopher S.; Al-Rasbi, Nawal K.; Ward, Michael D.; Lacour, Jérôme

doi:10.1039/b618092b

Cited by 53 publications

(24 citation statements)

References 52 publications

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“…TRISPHAT anion has been reported as an efficient NMR CSA for chiral quaternary phosphonium salts. 45 It has been possible to isolate the two ion pairs [(+)-(P)-1] [D-2] and [(À)-(M)-1][D-2] by using the cinchonidinium salt [Cincho + ][D-2] as CSA, for which the difference in 31 P NMR chemical shifts Dd = 0.78 ppm has been measured (Fig. of TRISPHAT, was 0.019 ppm.…”

Section: D-trisphat As Nmr Chiral Solvating Agentmentioning

confidence: 99%

“…Thus, TRISPHAT anion is found to probe the inherent chirality of the hemicryptophane host 1 through its interaction with the encaged cationic phosphorus. 45 It has been possible to isolate the two ion pairs [(+)-(P)-1] [D-2] and [(À)-(M)-1][D-2] by using the cinchonidinium salt [Cincho + ][D-2] as CSA, for which the difference in 31 P NMR chemical shifts Dd = 0.78 ppm has been measured ( Fig. 7).…”

Section: D-trisphat As Nmr Chiral Solvating Agentmentioning

confidence: 99%

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Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

et al. 2012

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The hemicryptophane racemate (±)-1 was optically resolved by semipreparative HPLC on Chiralpak IC column. The absolute configuration of each isolated enantiomer was established from the analysis of their electronic circular dichroism spectra. Enantiodifferentiation of the chiral cationic cage (±)-1 was evidenced in solution using Δ-TRISPHAT as chiral solvating agent, and the diastereomeric associations were observed in (1)H and (31)P NMR spectra.

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Section: D-trisphat As Nmr Chiral Solvating Agentmentioning

confidence: 99%

Section: D-trisphat As Nmr Chiral Solvating Agentmentioning

confidence: 99%

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

et al. 2012

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“…Addition of enantiopure anions Δ‐ 3 to complexes 21 led to the enantiodifferentiation of the ligands of the racemic salts and, more interestingly, of the achiral tetrafluoroborate anion trapped inside in the cage. The discrimination of the inside BF 4 − anion was even easier than that of the surrounding chiral cages (Δδ ∼2.0 and 0.4 ppm in 19 F and 1 H NMR, respectively) 23…”

Section: Successful Nmr Chiral Solvating Agentsmentioning

confidence: 99%

Hexacoordinated phosphates: how to teach old chiral anions new asymmetric tricks

Lacour

Linder

2007

The Chemical Record

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Chemical reactions and processes often involve chiral, yet racemic, cationic reagents, intermediates, or products. To afford instead nonracemic or enantiopure compounds, an asymmetric ion pairing of the cations with enantiopure anions can be considered—the counter ions behaving as asymmetric auxiliaries, ligands, or reagents. Detailed herein is a short review of our approach toward gaining reliable and predictable control over stereoselective ion pairing phenomena through the synthesis and use of novel configurationally stable hexacoordinated phosphate anions. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 275–285; 2007: Published online in Wiley InterScience (http://www.interscience.wiley.com) DOI 10.1002/tcr.20124

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“…60 In a similar approach, Ward and co-workers accomplished enantiodifferentiation of the ligands of the racemic salts of a [Co 4 (17) 6 (BF 4 )] 7+ cage (18; Figure 6a) by interaction with enantiopure ¦-TRISPHAT anion (Figure 6b). 59 Interestingly, the achiral encapsulated tetrafluoroborate anion was also observed to sense the influence of the diastereomeric ion pairs (Figure 6c).…”

Section: Diastereoselective Synthesismentioning

confidence: 99%

Stereochemical Communication within Tetrahedral Capsules

Ramsay¹,

Nitschke²

2013

Chemistry Letters

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The creation of isolated chirotopic environments that mimic enzyme binding pockets has been a long-term goal in supramolecular chemistry. Metalorganic cages with enclosed and defined inner spaces have proven useful for this purpose. Here, we provide a review of recent progress on understanding, and controlling the transmission of stereochemistry within [M 4 (L) 6 ] and [M 4 (L) 4 ] tetrahedral cages.

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Enantiodifferentiation of chiral cationic cages using trapped achiral BF4? anions as chirotopic probes

Abstract: The addition of enantiopure TRISPHAT anions to chiral cationic cages of type [Co 4 (L) 6 (BF 4 )] 7+ leads to the enantiodifferentiation of the ligands of the racemic salts and, even more effectively, of the achiral tetrafluoroborate anion trapped inside.

Cited by 53 publications

References 52 publications

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

Hexacoordinated phosphates: how to teach old chiral anions new asymmetric tricks

Stereochemical Communication within Tetrahedral Capsules

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