Cyclic arrays of five pyrenes on one rim of a planar chiral pillar[5]arene

Spatial arrangement of multiple planar chromophores is an emerging strategy for molecule-based chiroptical materials via easy and systematic synthesis. We attached five pyrene planes to a chiral macrocycle, pillar[5]arene, producing a set of chiroptical molecules in which pyrene-derived absorption and emission were endowed with dissymmetry by effective transfer of chiral information. The chiroptical response was dependent on linker structures and substituted patterns because of variable interactions between pyrene units. One of these hybrids showed larger dissymmetry factor and response wavelength (g_lum = 7.0 × 10⁻³ at ca. 547 nm) than reported pillar[5]arene-based molecules using the pillar[5]arene cores as parts of photo-responsive π-conjugated units.

Chirality of a C₅-symmetric pillar[5]arene was effectively transmitted to pyrene arrays in hybrid molecules. The pyrenes showed achiral monomer fluorescence and circularly polarized excimer emission.     

Tubularenes

We report the synthesis and characterization of conjugated, conformationally rigid, and electroactive carbon-based nanotubes that we term tubularenes. These structures are constructed from a resorcin[n_b]arene base. Cyclization of the conjugated aromatic nanotube is achieved in one-pot eight-fold C–C bond formation via Suzuki–Miyaura cross-coupling. DFT calculations indicate a buildup of strain energy in excess of 90 kcal mol⁻¹. The resulting architectures contain large internal void spaces >260 ų, are fluorescent, and able to accept up to 4 electrons. This represents the first scaffolding approach that provides conjugated nanotube architectures.

First scaffolding approach to obtain tubular-shaped contorted aromatic architectures.     

Upsurge in the construction of chiral nanomaterials

Owing to its fast development, chiral nanoscience has become one of the core research topics in chemistry, physics, medicine and materials science. Recently, many efforts have been focused on constructing new types of chiral nanomaterials with unique optical activity. This themed issue highlights the state-of-the art progress in this field, based on a series of invited and selected articles published in Chemical Science. These articles cover diverse nanomaterials, including organic, inorganic, organic–inorganic hybrid and superstructured nanomaterials. The details based on the composition are as follows:On the topic of organic nanomaterials, one can refer to Tomoki Ogoshi et al.’s work on constructing pillar[5]arene-based chiral nanotubes via pre-regulation of the building blocks’ chirality (DOI: 10.1039/D1SC00074H), the surface-induced enantiomorphic crystallization of achiral fullerene derivatives in thin films done by Keisuke Tajima et al. (DOI: 10.1039/D0SC01163K), and chiral polymer hosts for circularly polarized electroluminescence devices realized by Changsoon Kim, Youngmin You and coworkers (DOI: 10.1039/D1SC02095A).Specific to organic nanomaterials with chiral aggregate-induced emission (AIE) properties, Yanhua Cheng, Ben Zhong Tang and coworkers reported the polymorph selectivity of an AIE luminogen under nano-confinement to visualize polymer microstructures (DOI: 10.1039/C9SC04239C). Minghua Liu, Shimei Jiang and coworkers presented multicolor tunable circularly polarized luminescence in a single AIE system (DOI: 10.1039/C9SC05643B). Qinghua Lu, Hailiang Zhang, Quan Li and coworkers showed solvent polarity driven helicity inversion and circularly polarized luminescence in chiral AIE fluorophores (DOI: 10.1039/D0SC04179C). A corresponding review about the chiral assembly of organic luminogens with AIE properties was given by Hai-Tao Feng, Ben Zhong Tang and coworkers (DOI: 10.1039/D1SC02305E).On the topic of inorganic nanomaterials, Masahiro Ehara, Takuya Nakashima and coworkers reported enantioseparation and chiral induction in Ag₂₉ nanoclusters with intrinsic chirality (DOI: 10.1039/C9SC05299B). Yoshitaka Aramaki, Takashi Ooi, Masakazu Nambo, Cathleen M. Crudden and coworkers introduced the synthesis and enantioseparation of chiral Au₁₃ nanoclusters protected by bis-N-heterocyclic carbene ligands (DOI: 10.1039/D1SC03076K). Georg H. Mehl showed the development of two helices from one chiral center in self-organized disc-shaped chiral nanoparticles (DOI: 10.1039/D0SC05100D). A review on template-assisted self-assembly of achiral plasmonic nanoparticles into chiral structures was written by Luis M. Liz-Marzán (DOI: 10.1039/D1SC03327A).On the topic of organic–inorganic hybrid nanomaterials, Shu Kobayashi prepared heterogeneous Rh and Rh/Ag bimetallic nanoparticle catalysts immobilized on chiral polymers with high-to-excellent yields and enantioselectivities (DOI: 10.1039/C9SC02670C). Xiaogang Qu fabricated a series of stereoselective nanozymes (Fe₃O₄@poly(AA)) using a ferromagnetic nanoparticle yolk as the catalytic core and amino acid-appended chiral polymer shell as the chiral selector (DOI: 10.1039/D0SC03082A). Yongsheng Zhao, Chuanlang Zhan, Jiannian Yao and coworkers reported lanthanide MOFs for inducing the molecular chirality of achiral stilbazolium with strong circularly polarized luminescence and efficient energy transfer for color tuning (DOI: 10.1039/D0SC02856H).On the topic of superstructures, Zeyuan Dong constructed a helical supramolecular polymer nanotube by manipulating strong noncovalent interactions (DOI: 10.1039/C9SC02336D). De-Liang Long, Leroy Cronin and coworkers fabricated peptide sequence mediated molybdenum blue nanowheel superstructures (DOI: 10.1039/D0SC06098D). Kazuhiko Nakatani, Chikara Dohno, Ben L. Feringa and coworkers designed a photoswitchable DNA glue with high regulatory function and supramolecular chirality transfer (DOI: 10.1039/D1SC02194J). A related review of hierarchical self-assembly into chiral nanostructures was presented by Minghua Liu (DOI: 10.1039/D1SC03561D).The above articles and reviews provide a complete picture of the construction of various chiral nanomaterials. We hope that the readers will quickly grasp the entire concept of this field with the help of this themed issue.     

Pressure-driven,solvation-directed planar chirality switching of cyclophano-pillar[5]arenes (molecular universal joints)

Planar chiral cyclophanopillar[5]arenes with a fused oligo(oxyethylene) or polymethylene subring (MUJs), existing as an equilibrium mixture of subring-included (in) and -excluded (out) conformers, respond to hydrostatic pressure to exhibit dynamic chiroptical property changes, leading to an unprecedented pressure-driven chirality inversion and the largest ever-reported leap of anisotropy (g) factor for the MUJ with a dodecamethylene subring. The pressure susceptivity of MUJs, assessed by the change in g per unit pressure, is a critical function of the size and nature of the subring incorporated and the solvent employed. Mechanistic elucidations reveal that the in–out equilibrium, as the origin of the MUJ''s chiroptical property changes, is on a delicate balance of the competitive inclusion of subrings versus solvent molecules as well as the solvation of the excluded subring. The present results further encourage our use of pressure as a unique tool for dynamically manipulating various supramolecular devices/machines.

Pressure switches the in/out conformation of cyclophano-pillararenes with accompanying inversion of the chiroptical properties.     

Asymmetric systematic synthesis,structures, and (chir)optical properties of a series of dihetero[8]helicenes

A series of dihetero[8]helicenes have been systematically synthesized in enantiomerically enriched forms by utilizing the characteristic transformations of the organosulfur functionality. The synthetic route begins with assembling a ternaphthyl common synthetic intermediate from 2-naphthol and bissulfinylnaphthalene through an extended Pummerer reaction followed by facile multi-gram-scale resolution. The subsequent cyclization reactions into dioxa- and dithia[8]helicenes take place with excellent axial-to-helical chirality conversion. Dithia[8]helicene is further transformed into the nitrogen and the carbon analogs by replacing the two endocyclic sulfur atoms via S_NAr-based skeletal reconstruction. The efficient systematic synthesis has enabled comprehensive evaluation of physical properties, which has clarified the effect of the endocyclic atoms on their structures and (chir)optical properties as well as the unexpected conformational stability of the common helical framework.

A series of dihetero[8]helicenes have been synthesized in a stereoselective manner through an organosulfur-based synthetic strategy, which has enabled clarifying the effect of the endocyclic atoms on physical properties.     

Regiodivergent construction of medium-sized heterocycles from vinylethylene carbonates and allylidenemalononitriles

Medium-sized heterocycles exist in a broad spectrum of biologically active natural products and medicinally important synthetic compounds. The construction of medium-sized rings remains challenging, particularly the assembly of different ring sizes from the same type of substrate. Here we report palladium-catalyzed, regiodivergent [5 + 4] and [5 + 2] annulations of vinylethylene carbonates and allylidenemalononitriles. We describe the production of over 50 examples of nine- and seven-membered heterocycles in high isolated yields and excellent regioselectivities. We demonstrate the synthetic utility of this approach by converting a nine-membered ring product to an interesting polycyclic caged molecule via a [2 + 2] transannulation. Mechanistic studies suggest that the [5 + 2] annulation proceeds through palladium-catalyzed ring-opening/re-cyclization from the [5 + 4] adducts.

Here we report palladium-catalyzed, regiodivergent [5 + 4] and [5 + 2] annulations of vinylethylene carbonates and allylidenemalononitriles affording over 50 medium-sized heterocycles in high isolated yields with excellent regioselectivities.     

Metal-free tandem carbene N–H insertions and C–C bond cleavages

A metal-free C–H [5 + 1] annulation reaction of 2-arylanilines with diazo compounds has been achieved, giving rise to two types of prevalent phenanthridines via highly selective C–C cleavage. Compared to the simple N–H insertion manipulation of diazo, this method elegantly accomplishes a tandem N–H insertion/S_EAr/C–C cleavage/aromatization reaction, and the synthetic utility of this new transformation is exemplified by the succinct syntheses of trisphaeridine and bicolorine alkaloids.

A metal-free C–H [5 + 1] annulation reaction of 2-arylanilines with diazo compounds has been achieved, giving rise to two types of prevalent phenanthridines via highly selective C–C cleavage.     

Amplification of weak chiral inductions for excellent control over the helical orientation of discrete topologically chiral (M3L2)n polyhedra

Superb control over the helical chirality of discrete (M₃L₂)_n polyhedra (n = 2,4,8, M = Cu^I or Ag^I) created from the self-assembly of propeller-shaped ligands (L) equipped with chiral side chains is demonstrated here. Almost perfect chiral induction (>99 : 1) of the helical orientation of the framework was achieved for the largest (M₃L₂)₈ cube with 48 small chiral side chains (diameter: ∼5 nm), while no or moderate chiral induction was observed for smaller polyhedra (n = 2, 4). Thus, amplification of the weak chiral inductions of each ligand unit is an efficient way to control the chirality of large discrete nanostructures with high structural complexity.

Superb control over the helical chirality of highly-entangled (M₃L₂)_n polyhedra (M = Cu(i), Ag(i); n = 2,4,8) was achieved via multiplication of weak chiral inductions by side chains accumulated on the huge polyhedral surfaces.     

Discovery of an all-donor aromatic [2]catenane

We report herein the first all-donor aromatic [2]catenane formed through dynamic combinatorial chemistry, using single component libraries. The building block is a benzo[1,2-b:4,5-b′]dithiophene derivative, a π-donor molecule, with cysteine appendages that allow for disulfide exchange. The hydrophobic effect plays an essential role in the formation of the all-donor [2]catenane. The design of the building block allows the formation of a quasi-fused pentacyclic core, which enhances the stacking interactions between the cores. The [2]catenane has chiro-optical and fluorescent properties, being also the first known DCC-disulphide-based interlocked molecule to be fluorescent.

An all-donor [2]catenane has been synthesised via dynamic combinatorial chemistry. It features stacked benzodithiophenes which are quasi-pentacyclic through hydrogen bonding.     

Chiral Lewis acid-bonded picolinaldehyde enables enantiodivergent carbonyl catalysis in the Mannich/condensation reaction of glycine ester

A new strategy of asymmetric carbonyl catalysis via a chiral Lewis acid-bonded aldehyde has been developed for the direct Mannich/condensation cascade reaction of glycine ester with aromatic aldimines. The co-catalytic system of 2-picolinaldehyde and chiral Yb^III-N,N′-dioxides was identified to be efficient under mild conditions, providing a series of trisubstituted imidazolidines in moderate to good yields with high diastereo- and enantioselectivities. Enantiodivergent synthesis was achieved via changing the sub-structures of the chiral ligands. The reaction could be carried out in a three-component version involving glycine ester, aldehydes, and anilines with equally good results. Based on control experiments, the X-ray crystal structure study and theoretical calculations, a possible dual-activation mechanism and stereo-control modes were provided to elucidate carbonyl catalysis and enantiodivergence.

The catalytic asymmetric Mannich/condensation of glycine ester with aldimines was achieved by merging chiral N,N′-dioxide/Yb^III complex Lewis acid catalysis/carbonyl catalysis under mild condition.     

A chiral cobalt(ii) complex catalyzed enantioselective aza-Piancatelli rearrangement/Diels–Alder cascade reaction

A chiral N,N′-dioxide/cobalt(ii) complex catalyzed highly diastereoselective and enantioselective tandem aza-Piancatelli rearrangement/intramolecular Diels–Alder reaction has been disclosed. Various valuable hexahydro-2a,5-epoxycyclopenta[cd]isoindoles bearing six contiguous stereocenters have been obtained in good yields with excellent diastereo- and enantio-selectivities from a wide range of both readily available 2-furylcarbinols and N-(furan-2-ylmethyl)anilines.

An asymmetric aza-Piancatelli rearrangement/Diels–Alder cascade reaction between 2-furylcarbinols and N-(furan-2-ylmethyl)anilines was realized by using a chiral N,N′-dioxide/cobalt(ii) complex catalyst.     

On Raman optical activity sign-switching between the ground and excited states leading to an unusual resonance ROA induced chirality

Raman optical activity (ROA) spectra recorded for a chiral naphthalene diimide derivative (nBu-NDI–BINAM) dissolved in a series of solvents exhibit strong solute to solvent induced chirality with: (1) dominating bands of solvents, (2) nBu-NDI–BINAM resonance ROA (RROA) bands which are barely visible, (3) monosignate RROA Solvent spectra with an unexpected sign concordant with that of the ECD band of the resonant electronic state, (4) bisignate RROA bands for a few solvents, and (5) superposition of non-resonant and resonant ROA bands of the chiral solvents. The unusual ROA enhancement was explained in terms of resonance energy transfer with resonant Raman emission. The surprising RROA sign-switching was found to be due to specific conformational equilibria where one solute conformer dominates in the ground and the other in the first excited singlet state, and, the signs of the related ECD bands of these two conformers are opposite.

Unusual solute to solvent induced chirality in ROA comes from specific conformer equilibria in the ground and the excited states.     

Synthesis of novel pillar-shaped cavitands “Pillar[5]arenes” and their application for supramolecular materials

In 2008, we reported a new class of macrocyclic hosts and named “Pillar[5]arenes”. They combine the advantages and aspects of traditional hosts and have a composition similar to those of typical calix[n]arenes. Pillar[5]arenes have repeating units connected by methylene bridges at the para-position, and thus they have a unique symmetrical pillar architecture differing from the basket-shaped structure of meta-bridged calix[n]arenes. Pillar[5]arenes show high functionality similar to cyclodextrins, and can capture electron accepting guest molecules within their cavity similarly to cucurbit[n]urils. In this review, the synthesis, structure, rotation, host–guest properties, planar chirality and functionality of pillar[5]arenes are discussed, along with pillar[5]arene-based supramolecular architectures and the challenges in synthesizing pillar[6]arenes.     

Facile synthesis of axially chiral styrene-type carboxylic acids via palladium-catalyzed asymmetric C–H activation

A novel method by a one-step introduction of axial chirality and sterically hindered group has been developed for facile synthesis of axially chiral styrene-type carboxylic acids. With the palladium-catalyzed C–H arylation and olefination of readily available cinnamic acid established, this transformation demonstrated excellent yield, excellent stereocontrol (up to 99% yield and 99% ee), and broad substrate scope under mild conditions. The axially chiral styrene-type carboxylic acids produced have been successfully applied to Cp*Co^III-catalyzed asymmetric C–H activation reactions, indicating their potential as chiral ligands or catalysts in asymmetric synthesis.

Palladium-catalyzed asymmetric C–H functionalization to yield axially chiral styrene-type carboxylic acids is described, in which axial chirality and sterically hindered group were incorporated in one-step.     

Mechanism of diastereoisomer-induced chirality of BiOBr

Chiral molecule-driven asymmetric structures are known to be elusive because of the intriguing chirality transfer from chiral molecules to achiral species. Here, we found that the chiral assembly of BiOBr is independent of the chirality of the organic molecular inducer but dependent on geometric structural matching between the inducer and inorganic species. Diastereoisomeric sugar alcohols (DSAs) with identical numbers of carbon chiral centers and functional groups but with different R/S configurations and optical activities (OAs) were chosen as symmetry-breaking agents for inducing chiral mesostructured BiOBr films (CMBFs) under hydrothermal conditions. Multiple levels of chirality with different handedness were identified in the CMBFs. Density functional theory (DFT) calculations and molecular dynamics (MD) simulations suggest that asymmetric defects in the Br–Bi tetragonal cone caused by physically adsorbed DSAs on the surfaces of the BiOBr crystals are the geometric basis for triggering the chiral twist in the BiOBr monolayer. Our findings provide new insights for understanding the origin of chirality and the chiral transfer mechanism underlying the assembly of achiral species.

The chirality transfer is dependent on geometrical matching between the chiral inducer and inorganic species.     

Lanthanide MOFs for inducing molecular chirality of achiral stilbazolium with strong circularly polarized luminescence and efficient energy transfer for color tuning

We present herein an innovative host–guest method to achieve induced molecular chirality from an achiral stilbazolium dye (DSM). The host–guest system is exquisitely designed by encapsulating the dye molecule in the molecule-sized chiral channel of homochiral lanthanide metal–organic frameworks (P-(+)/M-(−)-TbBTC), in which the P- or M-configuration of the dye is unidirectionally generated via a spatial confinement effect of the MOF and solidified by the dangling water molecules in the channel. Induced chirality of DSM is characterized by solid-state circularly polarized luminescence (CPL) and micro-area polarized emission of DSM@TbTBC, both excited with 514 nm light. A luminescence dissymmetry factor of 10⁻³ is obtained and the photoluminescence quantum yield (PLQY) of the encapsulated DSM in DSM@TbTBC is ∼10%, which is close to the PLQY value of DSM in dilute dichloromethane. Color-tuning from green to red is achieved, owing to efficient energy transfer (up to 56%) from Ln³⁺ to the dye. Therefore, this study for the first time exhibits an elegant host–guest system that shows induced strong CPL emission and enables efficient energy transfer from the host chiral Ln-MOF to the achiral guest DSM with the emission color tuned from green to red.

Homochiral Ln-MOFs are synthesized to encapsulate achiral dyes to induce strong circularly polarized luminescence with a luminescence dissymmetry factor of 10⁻³.     

Rh(i)-catalyzed stereoselective desymmetrization of prochiral cyclohexadienones via highly exo-selective Huisgen-type [3 + 2] cycloaddition

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed. This method enables convergent construction of complex epoxy-bridged polycyclic ring systems with five contiguous stereocenters with excellent exo-selectivity and broad substrate scope. The highly atom-economical process involves 6-endo-dig cyclization of carbonyl oxygen onto an activated alkyne resulting in a highly reactive metal–benzopyrylium intermediate, which readily undergoes intramolecular [3 + 2] annulation/hydration. Asymmetric induction is also achieved for the first time in Rh(i)-catalyzed 1,3-dipolar cycloaddition using an easily accessible chiral diene as the ligand.

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed.     

Catalytic enantioselective synthesis of macrodiolides and their application in chiral recognition

New types of C₂-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.

An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex.     

Formal oxo- and aza-[3 + 2] reactions of α-enaminones and quinones: a double divergent process and the roles of chiral phosphoric acid and molecular sieves

A double divergent process has been developed for the reaction of α-enaminones with quinones through facile manipulation of catalyst and additive, leading to structurally completely different products. The two divergent processes, which involve formal aza- and oxo-[3 + 2] cycloaddition reactions, are mediated by chiral phosphoric acid and molecular sieves, respectively. While inclusion of phosphoric acid in the reaction switched the reaction pathway to favor the efficient formation of a wide range of N-substituted indoles, addition of 4 Å molecular sieves to the reaction switched the reaction pathway again, leading to enantioselective synthesis of 2,3-dihydrobenzofurans in excellent yields and enantioselectivities under mild conditions. Studies in this work suggest that the chiral phosphoric acid acts to lower the transition state energy and promote the formation of amide intermediate for the formal aza-[3 + 2] cycloaddition and the molecular sieves serve to facilitate proton transfer for oxo-[3 + 2] cycloaddition. The reactivity of α-enaminones is also disclosed in this work.

A double divergent process for [3 + 2] cycloadditions of α-enaminones with quinones led to the formation of N-substituted indoles and 2,3-dihydrobenzofurans.     

Palladium/Xu-Phos-catalyzed asymmetric carboamination towards isoxazolidines and pyrrolidines

An efficient palladium-catalyzed enantioselective carboamination reaction of N-Boc-O-homoallyl-hydroxylamines and N-Boc-pent-4-enylamines with aryl or alkenyl bromides was developed, delivering various substituted isoxazolidines and pyrrolidines in good yields with up to 97% ee. The reaction features mild conditions, general substrate scope and scalability. The obtained products can be transformed into chiral 1,3-aminoalcohol derivatives without erosion of chirality. The newly identified Xu-Phos ligand bearing an ortho-OⁱPr group is responsible for the good yield and high enantioselectivity.

The new chiral ligand (S,Rs)-Xu4 with ortho-OⁱPr showed good performance in the asymmetric carboamination reaction of N-Boc-O-homoallyl-hydroxylamines and N-Boc-pent-4-enylamines with aryl or alkenyl bromides.