Synthesis of the First Water-Soluble Hemicryptophane Host: Selective Recognition of Choline in Aqueous Medium

Schmitt, Aline; Robert, Vincent; Dutasta, Jean‐Pierre; Martinez, Alexandre

doi:10.1021/ol500706z

Cited by 23 publications

(24 citation statements)

References 46 publications

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“…These results can be compared to previous solution-phase results from three different perspectives. First, gas-phase results obtained for hemicryptophane 2 with choline and betaine guest molecules are consistent with those observed in solution [22]. Employing a very similar hemicryptophane cage that is water soluble, a selective recognition towards choline versus betaine was observed in solution [22].…”

Section: Discussionsupporting

confidence: 76%

“…The structure of a hemicryptophane molecule differs from a cryptophane cage in that one of the CTV caps is replaced with a C3-symmetrical organic group [20]. Hemicryptophanes have been employed for selective inclusion of choline [22], choline phosphate [23] or primary alkylammonium ions [24]. Moreover, hemicryptophanes have been used for enantioselective recognition [25,26] as well as ion-pair recognition [27] and studies pertaining to potential catalytic activity [28] have also been conducted.…”

Section: Introductionmentioning

confidence: 99%

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Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

Bayat

Gatineau

Lesage

et al. 2018

J. Am. Soc. Mass Spectrom.

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In advancing host-guest (H-G) chemistry, considerable effort has been spent to synthesize host molecules with specific and well-defined molecular recognition characteristics including selectivity and adjustable affinity. An important step in the process is the characterization of binding strengths of the H-G complexes that is typically performed in solution using NMR or fluorescence. Here, we present a mass spectrometry-based multimodal approach to obtain critical energies of dissociation for two hemicryptophane cages with three biologically-relevant guest molecules. A combination of blackbody infrared radiative dissociation (BIRD) and high-pressure collision induced dissociation (high-pressure CID), along with RRKM modeling, were employed for this purpose. For the two tested hemicryptophane hosts, the cage containing naphthyl linkages exhibited stronger interactions than the cage bearing phenyl linkages. For both cages, the order of guest stability is: choline > acetylcholine > betaine.The information obtained by these types of mass spectrometric studies can provide new insight into the structural features that most influence the stability of H-G pairs, thereby providing guidance for future syntheses.

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Section: Discussionsupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

Bayat

Gatineau

Lesage

et al. 2018

J. Am. Soc. Mass Spectrom.

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“…Gas‐phase investigation of H‐G systems is of great importance in providing information regarding their intrinsic structural and binding properties. Solution‐phase studies have shown that hemicryptophane cages of various types can exhibit binding selectivity toward suitable guests, resulting in encapsulation of the guest . However, the degree of encapsulation and the strength of H‐G binding in solution may be influenced by solvation and counter ion effects.…”

Section: Introductionmentioning

confidence: 99%

“…Solution-phase studies have shown that hemicryptophane cages of various types can exhibit binding selectivity toward suitable guests, resulting in encapsulation of the guest. 7,8,20,21,[26][27][28] However, the degree of encapsulation and the strength of H-G binding in solution may be influenced by solvation and counter ion effects. Gas phase studies, on the other hand, can provide a more direct means to probe intrinsic interactions between host and guest without the additional encumbrance of solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

et al. 2019

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A low‐energy collision induced dissociation (CID) (low‐energy CID) approach that can determine both activation energy and activation entropy has been used to evaluate gas‐phase binding energies of host‐guest (H‐G) complexes of a heteroditopic hemicryptophane cage host (Zn (II)@1) with a series of biologically relevant guests. In order to use this approach, preliminary calibration of the effective temperature of ions undergoing resonance excitation is required. This was accomplished by employing blackbody infrared radiative dissociation (BIRD) which allows direct measurement of activation parameters. Activation energies and pre‐exponential factors were evaluated for more than 10 H‐G complexes via the use of low‐energy CID. The relatively long residence time of the ions inside the linear ion trap (maximum of 60 s) allowed the study of dissociations with rates below 1 s−1. This possibility, along with the large size of the investigated ions, ensures the fulfilment of rapid energy exchange (REX) conditions and, as a consequence, accurate application of the Arrhenius equation. Compared with the BIRD technique, low‐energy CID allows access to higher effective temperatures, thereby permitting one to probe more endothermic decomposition pathways. Based on the measured activation parameters, guests bearing a phosphate (―OPO32−) functional group were found to bind more strongly with the encapsulating cage than those having a sulfonate (―SO3−) group; however, the latter ones make stronger bonds than those with a carboxylate (―CO2−) group. In addition, it was observed that the presence of trimethylammonium (―N(CH3)3+) or phenyl groups in the guest's structure improves the strength of H‐G interactions. The use of this technique is very straightforward, and it does not require any instrumental modifications. Thus, it can be applied to other H‐G chemistry studies where comparison of bond dissociation energies is of paramount importance.

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“…We thus focused on tren–hemicryptophanes containing the C 3 ‐symmetric tris(2‐aminoethyl)amine (tren) ligand, which exhibited substrate‐, diastereo‐, and enantioselective recognition properties toward neurotransmitters and carbohydrates ,. Moreover, encaged azatrane structures can be formed when a metal or heteroelement is introduced into the tren unit.…”

Section: Introductionmentioning

confidence: 99%

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

Lefevre

Zhang

Godart

et al. 2016

Chemistry A European J

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A convenient and efficient gram-scale synthesis for enantiopure hemicryptophane-tren (tren=tris(2-aminoethyl)amine) derivatives has been developed. The four-step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.

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Synthesis of the First Water-Soluble Hemicryptophane Host: Selective Recognition of Choline in Aqueous Medium

Cited by 23 publications

References 46 publications

Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

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