Switched enantioselectivity by solvent components and temperature in photocyclodimerization of 2-anthracenecarboxylate with 6 A ,6 X -diguanidio− γ -cyclodextrins

Yi, Jigao; Liang, Wenting; Wei, Xueqin; Yao, Jie; Yan, Zhiqiang; Su, Dan; Zhong, Zhihui; Gao, Guowei; Wu, Wanhua; Yang, Cheng

doi:10.1016/j.cclet.2017.05.004

Cited by 31 publications

(10 citation statements)

References 29 publications

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“…These conformational and architectural dissimilarities further condition the inclusion properties: 4 -dimer can host the adamantane carboxylate guest to form a 4 -dimer:AC stable ternary species whereas the same AC guest triggers 5 -dimer disruption. Interestingly, the synthetic approach is compatible with the incorporation of functional elements at the primary positions of the cyclooligosaccharide, e.g., cationic centers to modulate the reactivity of guests confined in the CD cavity (Wei et al, 2018; Yi et al, 2018) or to mediate nucleic acid condensation (Aranda et al, 2013; Martínez et al, 2013; Jiménez Blanco et al, 2016; Martínez-Negro et al, 2017; Przybylski et al, 2018). The possibility of implementing different supramolecular organization levels (e.g., clusterization and/or inclusion and/or spatiotemporal controlled dissociation) with aromatic clips offers then a valuable tool to program the behavior of monodisperse CD-based devices in biological environments for (bio)molecular encapsulation and controlled release.…”

Section: Resultsmentioning

confidence: 99%

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

et al. 2019

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The presence of a doubly-linked naphthylene clip at the O -2 I and O -3 II positions in the secondary ring of β-cyclodextrin (βCD) derivatives promoted their self-assembly into head-to-head supramolecular dimers in which the aromatic modules act either as cavity extension walls (if the naphthalene moiety is 1,8-disubstituted) or as folding screens that separate the individual βCD units (if 2,3-disubstituted). Dimer architecture is governed by the conformational properties of the monomer constituents, as determined by NMR, fluorescence, circular dichroism, and computational techniques. In a second supramolecular organization level, the topology of the assembly directs host-guest interactions and, reciprocally, guest inclusion impacts the stability of the supramolecular edifice. Thus, inclusion of adamantane carboxylate, a well-known βCD cavity-fitting guest, was found to either preserve the dimeric arrangement, leading to multicomponent species, or elicit dimer disruption. The ensemble of results highlights the potential of the approach to program self-organization and external stimuli responsiveness of CD devices in a controlled manner while keeping full diastereomeric purity.

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Section: Resultsmentioning

confidence: 99%

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

et al. 2019

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“…In 2018, Wu, Yang, et al also reported the photocyclodimerization of AC with the aid of 6 A ,6 X -diguanidio-γ-CDs [ 26 ]. The γ-CDs and AC could form stable 1:2 ternary complexes.…”

Section: Reviewmentioning

confidence: 99%

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

Zuo¹,

Velmurugan²,

Wang³

et al. 2021

Beilstein J. Org. Chem.

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Due to the unique characteristics of macrocycles (e.g., the ease of modification, hydrophobic cavities, and specific guest recognition), they can provide a suitable environment to realize photocatalysis via noncovalent interactions with different substrates. In this minireview, we emphasized the photochemical transformation and catalytic reactivity of different guests based on the binding with various macrocyclic hosts as well as on the role of macrocyclic-hosts-assisted hybrid materials in energy transfer. To keep the clarity of this review, the macrocycles are categorized into the most commonly used supramolecular hosts, including crown ethers, cyclodextrins, cucurbiturils, calixarenes, and pillararenes. This minireview not only summarizes the role that macrocycles play in photocatalytic reactions but also clarifies the photocatalytic mechanisms. Finally, the future research efforts and new pathways to apply macrocycles and supramolecular hybrid materials in photocatalysis are also discussed.

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“…It has been demonstrated that both γ‐CD and β‐CD can dramatically accelerate the photocyclodimerization of AC through pre‐organizing the AC molecule(s) encapsulated in the cavity of CDs and forming either 1 : 2 complex or stepwise 1 : 1 and 2 : 2 complexes, respectively [4a,14] . Since the excited molecules are unstable and susceptible to various internal and external factors, the stereoselectivity of the photocyclodimerization of AC could be manipulated by altering the external environment variants, such as temperature, [15] pressure, [15a] solvent, [3b,15b,c] pH, [16] irradiation wavelength, [15b,17] salt additives, [8,14,16b] etc. In particular, the chemical structure of the chiral host, plays a vital role in the enantiodifferentiating process of the photoreaction, which may crucially influence the population as well as enantioselectivity of the photoproducts [4b,k,15b,18] …”

Section: Introductionmentioning

confidence: 99%

Supramolecular Enantiodifferentiating Photocyclodimerization of 2‐Anthracenecarboxylic Acid Mediated by Bridged β‐Cyclodextrins: Critical Effects of the Host Structure, pH and Co‐Solvents

Wang

Rao

et al. 2021

Chemistry An Asian Journal

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Several sulfoxide‐ and sulfone‐bridged β‐cyclodextrin (CD) dimers were synthesized for mediating the enantiodifferentiating [4+4] photocyclodimerization of 2‐anthracenecarboxylic acid (AC). The complexation behavior of these chiral hosts with AC was investigated by UV‐vis, circular dichroism, fluorescence, and NMR spectroscopies and certified the formation of 1 : 1 and 1 : 2 host‐guest complexes. The product distribution and enantioselectivity of the photoreaction turned out to be a critical function of the chemical structure of bridged CDs. Comparing to the sulfur‐bridged 2AX−3GX β‐CD dimer 7, the conversion of the photolyzes with sulfoxide‐bridged was significantly improved, and the ee of cyclodimer 2 was remarkably increased from −82.8% with 7 to −96.7% with the sulfoxide‐bridged 2AX−3GX β‐CD dimer 8. The relative yields and ee values of the slipped cyclodimers 5 and 6 were greatly enhanced in the presence of 6 M CsCl. The reaction selectivity is susceptible to the pH variation of the aqueous buffer solution, demonstrating that the supramolecular photochirogenesis is controlled by multidimensional factors, including the chemical structure of the chiral host, solvent, and pH conditions.

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Switched enantioselectivity by solvent components and temperature in photocyclodimerization of 2-anthracenecarboxylate with 6 A ,6 X -diguanidio− γ -cyclodextrins

Cited by 31 publications

References 29 publications

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

Supramolecular Enantiodifferentiating Photocyclodimerization of 2‐Anthracenecarboxylic Acid Mediated by Bridged β‐Cyclodextrins: Critical Effects of the Host Structure, pH and Co‐Solvents

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