Regio- and Enantioselective Macrocyclization from Dynamic Imine Formation: Chemo- and Enantioselective Fluorescent Recognition of Lysine

Mao, Yifan; Davis, Stephanie; Pu, Lin

doi:10.1021/acs.orglett.3c02949

Cited by 4 publications

(2 citation statements)

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“… Treatment of the THF solution of the BINOL monoMOM ether with 3.2 equiv of n BuLi at 0 °C to room temperature followed by the addition of DMF gave the monoaldehyde compound ( S )- 263 in 62% yield over the three steps (Scheme ). This compound and its enantiomer served as the precursor to a variety of BINOL-aldehyde-based fluorescent probes such as compounds ( S , S )- 264 , ( S )- 265a , ( S )- 265b , and ( R , R , R )- 266 for the recognition of amino acids and metal ions.…”

Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

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Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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“…Yu et al [ 31 ] synthesized a small molecule gel based on BINOL phosphoric acid, which improved the gelation ability by complexing with Cu 2+ ; L -histidine was highly sensitive to the formed organometallic gel and caused it to undergo gel collapse, while D -histidine did not affect it, enabling the enantiomeric recognition of histidine. Pu et al [ 32 ] utilized the dynamic public chemistry of imines and found that the bis-aldehyde structure with BINOL as the substrate could undergo regioselective and enantioselective macrocyclization reactions with chiral diamines, whereas better enantioselectivity with Zn 2+ coordination allowed high chemoselectivity and enantioselectivity for lysine.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Nanotubes Based on Chiral H8-BINOL Modified with 1,2,3-Triazole to Recognize Bi3+ Efficiently by ICT Mechanism

Tao,

Guo,

Sun

et al. 2024

Micromachines

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A novel fluorescent “off” probe R-β-D-1 containing a 1,2,3-triazole moiety was obtained by the Click reaction with azidoglucose using H8-BINOL as a substrate, and the structure was characterized by 1H NMR and 13C NMR and ESI-MS analysis. The fluorescence properties of R-β-D-1 in methanol were investigated, and it was found that R-β-D-1 could be selectively fluorescently quenched by Bi3+ in the recognition of 19 metal ions and basic cations. The recognition process of Bi3+ by R-β-D-1 was also investigated by fluorescence spectroscopy, SEM, AFM, etc. The complex pattern of R-β-D-1 with Bi3+ was determined by Job’s curve as 1 + 1, and the binding constant Ka of R-β-D-1 and Bi3+ was valued by the Benesi–Hildebrand equation as 1.01 × 104 M−1, indicating that the binding force of R-β-D-1 and Bi3+ was medium. The lowest detection limit (LOD) of the self-assembled H8-BINOL derivative for Bi3+ was up to 0.065 µM. The mechanism for the recognition of Bi3+ by the sensor R-β-D-1 may be the intramolecular charge transfer effect (ICT), which was attributed to the fact that the N-3 of the triazole readily serves as an electron acceptor while the incorporation of Bi3+ serves as an electron donor, and the two readily undergo coordination leading to the quenching of fluorescence. The recognition mechanism and recognition site could be verified by DFT calculation and CDD (Charge Density Difference).

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Stimuli-Responsive Photoluminescent Molecular Tweezers for Highly Enantioselective Discrimination of Chiral Primary Amines

Zhang,

Li,

Cheng

et al. 2024

Anal. Chem.

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To address the challenge of chiral recognition in terms of efficiency and generality, we propose a novel fluorescence sensing approach by rationally designing metal-ion-responsive chiral molecular tweezers. The flexible and adaptable molecular tweezers enable facile recognition of 31 structurally varied chiral primary amine compounds, including amino acids, amino acid esters, and chiral amines. Notably, upon stimulation by zinc ions, the chiral molecular tweezers demonstrate a higher enantioselective fluorescence response. Combined density functional theory calculations reveal that the chiral sensing mechanism relies on differential reaction rates and potential hydrogen-bonding interactions between the two enantiomers and the chiral receptor, which results in one of the enantiomers forming a more abundant, stable, and structurally rigid complex with the receptor, resulting in a significant increase in the fluorescence intensity and enantioselectivity. The stimuli-responsive molecular tweezers approach provides a novel strategy for precise stereocontrol and universality of chiral recognition, offering a promising tool for applications in various fields.

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Regio- and Enantioselective Macrocyclization from Dynamic Imine Formation: Chemo- and Enantioselective Fluorescent Recognition of Lysine

Cited by 4 publications

References 50 publications

Regioselective Substitution of BINOL

Regioselective Substitution of BINOL

Self-Assembled Nanotubes Based on Chiral H8-BINOL Modified with 1,2,3-Triazole to Recognize Bi3+ Efficiently by ICT Mechanism

Stimuli-Responsive Photoluminescent Molecular Tweezers for Highly Enantioselective Discrimination of Chiral Primary Amines

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