As a machine-recognizable representation of polymer connectivity, BigSMILES line notation extends SMILES from deterministic to stochastic structures. The same framework that allows BigSMILES to accommodate stochastic covalent connectivity can be extended to non-covalent bonds, enhancing its value for polymers, supramolecular materials, and colloidal chemistry. Non-covalent bonds are captured through the inclusion of annotations to pseudo atoms serving as complementary binding pairs, minimal key/value pairs to elaborate other relevant attributes, and indexes to specify the pairing among potential donors and acceptors or bond delocalization. Incorporating these annotations into BigSMILES line notation enables the representation of four common classes of non-covalent bonds in polymer science: electrostatic interactions, hydrogen bonding, metal–ligand complexation, and π–π stacking. The principal advantage of non-covalent BigSMILES is the ability to accommodate a broad variety of non-covalent chemistry with a simple user-orientated, semi-flexible annotation formalism. This goal is achieved by encoding a universal but non-exhaustive representation of non-covalent or stochastic bonding patterns through syntax for (de)protonated and delocalized state of bonding as well as nested bonds for correlated bonding and multi-component mixture. By allowing user-defined descriptors in the annotation expression, further applications in data-driven research can be envisioned to represent chemical structures in many other fields, including polymer nanocomposite and surface chemistry.
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Anion-binding catalyst designs for enantioselective synthesis
Select hydrogen bond donors can catalyze reactions of ion pairs through the recognition of anions. This mode of action can be exploited in enantioselective catalysis if a suitable chiral hydrogen bond donor is applied. Beyond just anionic recognition, an enantioselective anion-binding catalyst often must host numerous non-covalent interactions, including hydrogen bonding, general base, π-π, and π-cation, to achieve high levels of enantiocontrol. Anion-binding catalysts can be strategically designed to support those non-covalent interactions required to render a process highly stereoselective. Tactics applied in anion-binding catalyst development include enhancing arene substituents for improved π-stacking, linking two anion-binding units together on a single scaffold, expanding types of functional groups for anion recognition, and building frameworks with bifunctional modes of action. The intent of this digest is to highlight observations that suggest as anion-binding catalyst designs advance, their associated synthetic methodologies for complex molecule construction become increasingly impressive.
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- Award ID(s):
- 1362030
- NSF-PAR ID:
- 10054917
- Date Published:
- Journal Name:
- Tetrahedron letters
- Volume:
- 58
- Issue:
- 27
- ISSN:
- 0040-4039
- Page Range / eLocation ID:
- 2623-2628
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Affinities of six anions (mesylate, acetate, trifluoroacetate,
p ‐toluenecarboxylate,p ‐toluenesulfonate, and perfluorooctanoate) for three related Pt2+‐linked porphyrin nanocages were measured to probe the influence of different noncovalent recognition motifs (e. g., hydrogen bonding, electrostatics, π bonding) on anion binding. Two new hosts of M6L312+(1b ) and M4L28+(2 ) composition (M=(en)Pt2+, L=(3‐py)4porphyrin) were prepared in a one‐pot synthesis and allowed comparison of hosts that differ in structure while maintaining similar N−H hydrogen‐bond donor ability. Comparisons of isostructural hosts that differ in hydrogen‐bonding ability were made between1b and a related M6L312+nanoprism (1a , M=(tmeda)Pt2+) that lacks N−H groups. Considerable variation in association constants (K 1=1.6×103 M−1to 1.3×108 M−1) and binding mode (exo vs.endo ) were found for different host–guest combinations. Strongest binding was seen betweenp ‐toluenecarboxylate and1b , but surprisingly, association of this guest with1a was only slightly weaker despite the absence of NH⋅⋅⋅O interactions. The high affinity betweenp ‐toluenecarboxylate and1a could be turned off by protonation, and this behavior was used to toggle between the binding of this guest and the environmental pollutant perfluorooctanoate, which otherwise has a lower affinity for the host. -
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Abstract Synthetic chiral platforms can be a powerful platform for enantioselective interactions, especially when coupled with redox‐mediated electrochemical processes. While metallopolymers are versatile platforms for molecularly selective binding, their application for chiral applications is limited. In particular, the recognition and separation of biologically relevant chiral molecules can be key for biomanufacturing and diagnostics. Here, the design of chiral redox‐polymers enables electrochemically‐controlled enantioselective interactions, and supramolecular chirality is leveraged for enhancing recognition towards target enantiomers. Chiral redox‐metallopolymers are synthesized based on Ugi's amine‐inspired chiral monomers, and their enantioselective recognition toward ionic enantiomers such as tryptophan and naproxen is demonstrated, with higher enanhcement provided by the chiral redox‐polymer over the single‐site, chiral building bloack itelf. 2D nuclear magnetic resonance spectroscopy and solid‐state circular dichroism support the emergence of supramolecular chirality resulting from the intramolecular interaction between the ferrocene and the alkyl group in the backbone. The half potential shift of the redox‐polymers behaves linearly from 0% to 100%ee
l ‐tryptophan to enable enantiomer quantification. Investigation on solvent polarity and pH effect reveal that the enantioselective mechanism is attributed to the subtle balance between hydrogen bonding and π–π interaction. This study highlights the potential of chiral redox‐metallopolymers as platforms for electrochemically‐modulated enantioselective interactions towards a range of amino acids and pharmaceutical carboxylates. -
The use of chiral square planar gold( iii ) complexes to access enantioenriched products has rarely been applied in asymmetric catalysis. In this context, we report a mechanistic and synthetic investigation into the use of N-heterocyclic (NHC) gold( iii ) complexes in γ,δ-Diels–Alder reactions of 2,4-dienals with cyclopentadiene. The optimal catalyst bearing a unique 2-chloro-1-naphthyl substituent allowed efficient synthesis of functionally rich carbocycles in good yields, diastereo- and enantioselectivities. Transition state and multivariate linear regression (MLR) analysis of both catalyst and substrate trends using molecular descriptors derived from designer parameter acquisition platforms, reveals attractive non-covalent interactions (NCIs) to be key selectivity determinates. These analyses demonstrate that a putative π–π interaction between the substrate proximal double bond and the catalyst aromatic group is an essential feature for high enantioselectivity.more » « less
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Abstract Vinylogous urethane (VUO) based polymer networks are widely used as catalyst‐free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VUN) undergo much faster bond exchange than VUOand are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VUOand VUNvitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VUOand VUNlinkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VUOvitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VUN, these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea ‐ urethane (VU) network of strong non‐covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks.
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Accepted Manuscript1.0
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