Unidirectional complexation of pillar[4]arene[1]benzoquinoneoxime with alkyl alcohols

Li, Kun-Ang; Wang, Zhuo; Xie, Chang-Dong; Chen, Tao; Qiang, Hui; Liu, Yahu A.; Jia, Xueshun; Hu, Weibo; Wen, Ke

doi:10.1039/c9ob00665f

Cited by 8 publications

(4 citation statements)

References 43 publications

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“…Our group has previously developed unique methods to grow functional substituents on the rims of pillar[ n ]arenes. − We speculated that a pillar[ n ]arene-derived protein binding pocket mimetic could be realized through mounting a polar functionality on the rim of a pillar[ n ]arene and then forcing it to point toward the tubular core through either a steric effect or a substrate-induced conformational change. We therefore started our work from adding a small polar functionality, hydroxyl group, to the rim of pillar[5]arene by creating a quaternary carbon atom through a nucleophilic addition reaction of pillar[4]arene[1]quinone ( P4Q ) with phenylmagnesium chloride (or phenyllithium) (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 99%

Pillar[5]arene-Derived endo-Functionalized Molecular Tube for Mimicking Protein–Ligand Interactions

et al. 2021

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Arti cial tubular molecular pockets bearing polar functionalities on their inner surface are useful model systems for understanding the mechanisms of protein-ligand interactions in living systems. We herein report a pillar [5]arene-derived molecular tube, [P4-(OH)BPO], whose endo conformational isomer endo-[P4-(OH)BPO] possesses an inwardly pointing hydrogen-bond (H-bond) donor (OH) in its deep cavity, a strong H-bond acceptor (C=O) on the predominantly hydrophobic inner surface, rendering it a perfect protein binding pocket mimetic. By measuring the binding a nity of this pocket-mimetic tube, we screened a library of various shape-complementary organic guests (1-38) resembling the fragment ligands in fragment-based drug design (FBDD). On the basis of the data for "fragment-pocket" complexes (1-38)⊂endo-[P4-(OH)BPO], two rationally designed "lead molecules" (39 and 40) were identi ed to be able to enhance binding a nity signi cantly by forming H-bonds with both the donor and acceptor of endo-[P4-(OH)BPO]. The described work opens new avenues for developing pillar[n]arene-derived protein binding pocket-mimetic systems for studies on protein-ligand interactions and mechanisms of enzymatic reactions.

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Section: Results and Discussionmentioning

confidence: 99%

Pillar[5]arene-Derived endo-Functionalized Molecular Tube for Mimicking Protein–Ligand Interactions

et al. 2021

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“…Early in the development of the chemistry of the mechanical bond, Schill recognized that when a macrocycle containing a prochiral center such that its faces are distinguishable encircles an axle with distinguishable ends, the rotaxane can exist as distinct geometric isomers even though the individual components are stereochemically trivial . Although molecules that correspond to the type 1 mechanical geometric isomers (MGI-1) of rotaxanes have been reported, the vast majority where the mechanical bond provides the sole stereogenic unit are constructed from calixarenes or similar macrocycles whose facial dissymmetry arises from the fixed cone-shaped conformation of the threaded ring . The same is true of the corresponding catenane stereogenic unit first reported by Gaeta and Neri .…”

Section: Introductionmentioning

confidence: 94%

Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

Gallagher,

Savoini,

Saady

et al. 2024

J. Am. Chem. Soc.

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In 1971, Schill recognized that a prochiral macrocycle encircling an oriented axle led to geometric isomerism in rotaxanes. More recently, we identified an overlooked chiral stereogenic unit in rotaxanes that arises when a prochiral macrocycle encircles a prochiral axle. Here, we show that both stereogenic units can be accessed using equivalent strategies, with a single weak stereodifferentiating interaction sufficient for moderate to excellent stereoselectivity. Using this understanding, we demonstrated the first direct enantioselective (70% ee) synthesis of a mechanically axially chiral rotaxane.

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“…Most MGI-1 rotaxanes 48 and all reported MGI catenanes 49 are derived from calixarene or similar 50 macrocycles, where the facial dissymmetry is provided by a fixed cone-shaped conformation. Systems where the facial dissymmetry is provided by a single prochiral center, as proposed by Schill, 11 have been largely 51 overlooked.…”

Section: Mgi Catenanes and Rotaxanes (Type 1)mentioning

confidence: 99%

The End of the Beginning of Mechanical Stereochemistry

Goldup

2024

Acc. Chem. Res.

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Conspectus Stereochemistry has played a key role in the development of synthetic chemistry for the simple reason that the function and properties of most molecules, from medicine to materials science, depend on their shape and thus the stereoisomer used. However, despite the potential for rotaxanes and catenanes to display unusual forms of stereochemistry being identified as early as 1961, this aspect of the mechanical bond remained underexplored and underexploited; until 2014 it was only possible to access chiral rotaxanes and catenanes whose stereoisomerism is solely attributable to the mechanical bond using chiral stationary phase high performance liquid chromatography, which limited their production on scale and thus inhibited the investigation of their properties and applications. Furthermore, the stereogenic units of such molecules and analogues were often poorly described, which made it hard to fully articulate both what had been achieved in the field and what problems were left to solve. Relatively recently, methods to access rotaxanes and catenanes that display mechanical stereochemistry selectively have been developed, making these intriguing structures available for study in a range of prototypical applications including catalysis, sensing, and as chiral luminophores. In this Account, we briefly discuss the history of mechanical stereochemistry, beginning in 1961 when the potential for mechanical stereoisomerism was first identified, before defining how mechanical stereochemistry arises from a structural point of view. Building on this, using simple stereochemical arguments, we confirm that the complete set of unique stereogenic units of two-component rotaxanes and catenanes have finally been identified and categorized unambiguously, with the last being identified only in 2024. After pausing to discuss some of the stereochemical curiosities that arise when molecules contain both covalent and mechanical stereogenic units, and the potential for stereoisomerism to arise due to co-conformational movement, we use our stereochemical framework to summarize our efforts to develop conceptually general approaches to [2]catenanes and [2]rotaxanes containing all of the possible mechanical stereogenic units. In particular, we highlight how the nature of a mechanical stereogenic unit affects the available strategies for their stereoselective synthesis. We finish by highlighting recent prototypical chemical applications of interlocked molecules that rely on their mechanical stereochemistry, before discussing future directions and challenges. Taken together, we propose that the transition of such molecules from being hard to make and poorly described, to being available in high stereopurity using clearly articulated methodological and stereochemical concepts suggests that the field is finally maturing. Thus, we are now coming to the end of the beginning of mechanical stereochemistry. The stage is now set for such molecules to play a functional role in a range of areas, indeed in any chemical or physical application wh...

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Unidirectional complexation of pillar[4]arene[1]benzoquinoneoxime with alkyl alcohols

Abstract: Unidirectional binding between a pillar[4]arene[1]benzoquinoneoxime host and n-alkyl alcoholic guests was realized with the hydroxy heads of the guests in direct contact with the oxime group of the macrocyclic host.

Cited by 8 publications

References 43 publications

Pillar[5]arene-Derived endo-Functionalized Molecular Tube for Mimicking Protein–Ligand Interactions

Pillar[5]arene-Derived endo-Functionalized Molecular Tube for Mimicking Protein–Ligand Interactions

Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

The End of the Beginning of Mechanical Stereochemistry

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