Dynamic Control of Chiral Space Through Local Symmetry Breaking in a Rotaxane Organocatalyst.

We report on a switchable rotaxane molecular shuttle that features a pseudo-meso 2,5-disubstituted pyrrolidine catalytic unit on the axle whose local symmetry is broken according to the position of a threaded benzylic amide macrocycle. The macrocycle can be selectively switched (with light in one direction; with catalytic acid in the other) with high fidelity between binding sites located to either side of the pyrrolidine unit. The position of the macrocycle dictates the facial bias of the rotaxane-catalyzed conjugate addition of aldehydes to vinyl sulfones. The pseudo-meso non-interlocked thread does not afford significant selectivity as a catalyst (2-14% ee), whereas the rotaxane affords selectivities of up to 40% ee with switching of the position of the macrocycle changing the handedness of the product formed (up to 60% Δee).

• Publication year

  2019

• Venue

  Angewandte Chemie

• Publication date

  2019-09-09

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/anie.201908330PMID 31454135
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Structure Property Analysis of the Solution and Solid-State Properties of Bistable Photochromic Hydrazones.

  2019cited by this paper
• Recent Advances in the Synthesis and Application of Hydrogen Bond Templated Rotaxanes and Catenanes

  2019cited by this paper
• Double vision

  2019cited by this paper
• New Acylhydrazone Photoswitches with Quantitative Conversion and High Quantum Yield but without Hydrogen Bond Stabilizing ( Z)-Isomer.

  2019cited by this paper
• Evaluating continuous chirality measure as a 3D descriptor in chemoinformatics applied to asymmetric catalysis.

  2019cited by this paper
• Thinking Outside the "Blue Box": Induced Fit within a Unique Self-Assembled Polycationic Cyclophane.

  2019cited by this paper
• Dissipative Catalysis with a Molecular Machine

  2019cited by this paper
• Isoselective Lactide Ring Opening Polymerisation using [2]Rotaxane Catalysts

  2019cited by this paper
• Interlocking the Catalyst: Thread versus Rotaxane-Mediated Enantiodivergent Michael Addition of Ketones to β-Nitrostyrene.

  2019cited by this paper
• Chirality in rotaxanes and catenanes

  2018cited by this paper
• Chiral Mechanically Interlocked Molecules – Applications of Rotaxanes, Catenanes and Molecular Knots in Stereoselective Chemosensing and Catalysis

  2018cited by this paper
• Molecular machines for catalysis

  2018cited by this paper
• An artificial molecular machine that builds an asymmetric catalyst

  2018cited by this paper
• Molecular machines with bio-inspired mechanisms

  2018cited by this paper
• Enantioselective Formation of 2-Azetidinones by Ring-Assisted Cyclization of Interlocked N-(α-Methyl)benzyl Fumaramides.

  2018cited by this paper
• Building Strain with Large Macrocycles and Using It To Tune the Thermal Half-Lives of Hydrazone Photochromes.

  2018cited by this paper
• Mechanisch verzahnte Moleküle (MIMs) – molekulare Shuttle, Schalter und Maschinen (Nobel‐Aufsatz)

  2017cited by this paper
• Die Kunst, klein zu bauen: von molekularen Schaltern bis zu Motoren (Nobel‐Aufsatz)

  2017cited by this paper
• Sequence-Specific β-Peptide Synthesis by a Rotaxane-Based Molecular Machine.

  2017cited by this paper
• Von der chemischen Topologie zu molekularen Maschinen (Nobel‐Aufsatz)

  2017cited by this paper
• Photoswitchable interlocked thiodiglycolamide as a cocatalyst of a chalcogeno-Baylis–Hillman reaction

  2017cited by this paper
• From Chemical Topology to Molecular Machines (Nobel Lecture).

  2017cited by this paper
• Functional Mechanically Interlocked Molecules: Asymmetric Organocatalysis with a Catenated Bifunctional Brønsted Acid.

  2017cited by this paper
• Switching between Anion-Binding Catalysis and Aminocatalysis with a Rotaxane Dual-Function Catalyst.

  2017cited by this paper
• Pyridyl-Acyl Hydrazone Rotaxanes and Molecular Shuttles.

  2017cited by this paper
• Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

  2017cited by this paper
• Networking Nanoswitches for ON/OFF Control of Catalysis.

  2017cited by this paper
• A complementary pair of enantioselective switchable organocatalysts† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02462b Click here for additional data file.

  2017cited by this paper
• Mechanically Interlocked Molecules (MIMs)-Molecular Shuttles, Switches, and Machines (Nobel Lecture).

  2017cited by this paper
• Stereodivergent synthesis with a programmable molecular machine

  2017cited by this paper
• Nanotechnology: A molecular assembler

  2017cited by this paper
• Induction of Single-Handed Helicity of Polyacetylenes Using Mechanically Chiral Rotaxanes as Chiral Sources.

  2017cited by this paper
• The Art of Building Small: From Molecular Switches to Motors (Nobel Lecture).

  2017cited by this paper
• Pick-up, transport and release of a molecular cargo using a small-molecule robotic arm.

  2016cited by this paper
• Dynamic Responsive Systems for Catalytic Function.

  2016cited by this paper
• Refoldable Foldamers: Global Conformational Switching by Deletion or Insertion of a Single Hydrogen Bond

  2016cited by this paper
• Asymmetric Catalysis with a Mechanically Point-Chiral Rotaxane

  2016cited by this paper
• A Fluorescent and Switchable Rotaxane Dual Organocatalyst.

  2016cited by this paper
• Tying a Molecular Overhand Knot of Single Handedness and Asymmetric Catalysis with the Corresponding Pseudo-D3-Symmetric Trefoil Knot

  2016cited by this paper
• Genesis of the Nanomachines: The 2016 Nobel Prize in Chemistry.

  2016cited by this paper
• Die Genese der Nanomaschinen: der Chemie‐Nobelpreis 2016

  2016cited by this paper
• Stereocontrolled Synthesis of β-Lactams within [2]Rotaxanes: Showcasing the Chemical Consequences of the Mechanical Bond.

  2016cited by this paper
• Artificial switchable catalysts.

  2015cited by this paper
• A Stimuli-Responsive Rotaxane–Gold Catalyst: Regulation of Activity and Diastereoselectivity

  2015cited by this paper
• Acylhydrazones as Widely Tunable Photoswitches.

  2015cited by this paper
• Artificial Molecular Machines

  2015cited by this paper
• Rise of the Molecular Machines

  2015cited by this paper
• Goldberg Active Template Synthesis of a [2]Rotaxane Ligand for Asymmetric Transition-Metal Catalysis.

  2015cited by this paper
• Dynamic control of chirality in phosphine ligands for enantioselective catalysis

  2015cited by this paper
• Die Evolution molekularer Maschinen

  2015cited by this paper
• A switchable [2]rotaxane asymmetric organocatalyst that utilizes an acyclic chiral secondary amine.

  2014cited by this paper
• Dual stereocontrol over the Henry reaction using a light- and heat-triggered organocatalyst.

  2014cited by this paper
• Selecting reactions and reactants using a switchable rotaxane organocatalyst with two different active sites† †Electronic supplementary information (ESI) available: Synthetic procedures and characterisation data. See DOI: 10.1039/c4sc03279a Click here for additional data file.

  2014cited by this paper
• Exploring the activation modes of a rotaxane-based switchable organocatalyst.

  2014cited by this paper
• Efficient assembly of threaded molecular machines for sequence-specific synthesis.

  2014cited by this paper
• A light-induced reversible phase separation and its coupling to a dynamic library of imines

  2014cited by this paper
• Sequence-Specific Peptide Synthesis by an Artificial Small-Molecule Machine

  2013cited by this paper
• A switching cascade of hydrazone-based rotary switches through coordination-coupled proton relays

  2012cited by this paper
• A three-compartment chemically-driven molecular information ratchet.

  2012cited by this paper
• A rotaxane-based switchable organocatalyst.

  2012cited by this paper
• A redox-reconfigurable, ambidextrous asymmetric catalyst.

  2012cited by this paper
• Dynamic Control of Chiral Space in a Catalytic Asymmetric Reaction Using a Molecular Motor

  2011cited by this paper
• Switching around two axles: controlling the configuration and conformation of a hydrazone-based switch.

  2011cited by this paper
• Configurational and constitutional information storage: multiple dynamics in systems based on pyridyl and acyl hydrazones.

  2011cited by this paper
• Switching through coordination-coupled proton transfer.

  2011cited by this paper
• High-molecular-weight polyquinoxaline-based helically chiral phosphine (PQXphos) as chirality-switchable, reusable, and highly enantioselective monodentate ligand in catalytic asymmetric hydrosilylation of styrenes.

  2010cited by this paper
• Thiazolium-Tethering Rotaxane-Catalyzed Asymmetric Benzoin Condensation: Unique Asymmetric Field Constructed by the Cooperation of Rotaxane Components

  2010cited by this paper
• Highly enantioselective conjugate additions of aldehydes to vinyl sulfones.

  2009cited by this paper
• A chemically-driven molecular information ratchet.

  2008cited by this paper
• Recent progress on switchable rotaxanes.

  2006cited by this paper
• First organocatalyzed asymmetric Michael addition of aldehydes to vinyl sulfones.

  2005cited by this paper
• Asymmetric benzoin condensation catalyzed by chiral rotaxanes tethering a thiazolium salt moiety via the cooperation of the component: can rotaxane be an effective reaction field?

  2004cited by this paper
• Synthesis and application of chiral P,N-ligands with pseudo-meso and pseudo-C(2) symmetry.

  2001cited by this paper
• Peptide-Based Molecular Shuttles

  1997cited by this paper
• Anion‐Assisted Self‐Assembly

  1997cited by this paper
• DESIGNING A RECEPTOR FOR MOLECULAR RECOGNITION IN A CATALYTIC SYNTHETIC REACTION : ALLYLIC ALKYLATION

  1996cited by this paper
• A chemically and electrochemically switchable molecular shuttle

  1994cited by this paper

• Amino-acid-encoded assembly of programmable chiral Solomon links

  2026cites this paper
• Rotaxanes with integrated photoswitches: design principles, functional behavior, and emerging applications

  2025cites this paper
• Structure-performance relationships for catalysis-driven molecular machinery

  2025cites this paper
• Bis-subporphyrin-like boron(iii) complexes derived from indolo[2,3-a]carbazole-based cyclic bis-BODIPYs exhibiting persistent helical chirality

  2025cites this paper
• (Supra)Molecular Switches Controlled by Artificial Signaling Cascades

  2025cites this paper
• Phosphorus-Nitrogen Compounds: Part 76. Design and Syntheses of Dispiro- and Trispiro(N/N)cyclotriphosphazenes: Conformational and Structural Analyses, Chirality, Electrochemical, Dye-Sensitized Solar Cells, and Bioactivity Studies.

  2024cites this paper
• Changing Liquid Crystal Helical Pitch with a Reversible Rotaxane Switch.

  2024cites this paper
• Macroscopic spiral rotation of microscopic objects induced by nanoscale rotaxane dynamics

  2024cites this paper
• Effect of Counterion Size on Knotted Polyelectrolyte Conformations.

  2024cites this paper
• [5]Molecular Necklaces Formed Through Zn2+-Templated Binding of Macrocycles to Dynamically Formed Imines as Guest Recognition Sites.

  2024cites this paper
• Switchable supramolecular helices for asymmetric stereodivergent catalysis

  2024cites this paper
• Conjugated bis(enaminones) as effective templates for rotaxane assembly and their post-synthetic modifications

  2024cites this paper
• Steric Engineering of Rotaxane Catalysts: Benefits and Limits of Using the Mechanical Bond in Catalyst Design.

  2024cites this paper
• Heterobifunctional rotaxanes featuring two chiral subunits - synthesis and application in asymmetric organocatalysis.

  2024cites this paper
• Switchable Topologically Chiral [2]Catenane as Multiple Resonance Thermally Activated Delayed Fluorescence Emitter for Efficient Circularly Polarized Electroluminescence.

  2024cites this paper
• Synthesis and Characterization of Photoswitchable Dithienylethene-Based Chiral Bisoxazoline Compounds with Bidirectional Visible Light Control.

  2023cites this paper
• An Anion-Switchable Dual-Function Rotaxane Catalyst.

  2023cites this paper
• Enantiodivergent Sulfoxidation Catalyzed by a Photoswitchable Iron Salen Phosphate Complex.

  2023cites this paper
• Molecular Hinges by Fusion of Pyrrole and Dithiin: Synthesis, Structure, Redox Chemistry and Host-guest Complexation of Dipyrrolo-1,4-dithiins.

  2023cites this paper
• Traffic Lights for Catalysis: Stimuli-Responsive Molecular and Extended Catalytic Systems.

  2023cites this paper
• "Cage Walking" Synthetic Strategy for Unusual Unsymmetrical Supramolecular Cages.

  2023cites this paper
• Self-sorting as a versatile strategy in the synthesis of rotaxanes and catenanes

  2023cites this paper
• The use of molecular electronic structure methods to investigate mechanically interlocked molecules.

  2023cites this paper
• Topological Entanglement of Linear Catenanes: Knots and Threadings

  2023cites this paper
• Mechanically Interlocked Biomacromolecules

  2023cites this paper
• Two Squares in a Barrel: An Axially Disubstituted Conformationally Rigid Aliphatic Binding Motif for Cucurbit[6]uril

  2023cites this paper
• Artificial molecular machines: Design and observation

  2023cites this paper
• Emerging properties from mechanical tethering within a post-synthetically functionalised catenane scaffold

  2022cites this paper
• Mechanically axially chiral catenanes and noncanonical mechanically axially chiral rotaxanes

  2022cites this paper
• Metal-Ion-Induced Mechanical Chirality: Achiral Rotaxane as the Only Ligand in Chiral Palladium(II)-N-Heterocyclic Carbene Complexes.

  2022cites this paper
• Enantiodivergent epoxidation of alkenes with a photoswitchable phosphate manganese-salen complex

  2022cites this paper
• Recent Progress in Light-Driven Molecular Shuttles

  2022cites this paper
• Controlling catalyst activity, chemoselectivity and stereoselectivity with the mechanical bond

  2022cites this paper
• Rhodium-Catalyzed ON-OFF Switchable Hydrogenation Using a Molecular Shuttle based on a [2]Rotaxane with a Phosphine Ligand.

  2022cites this paper
• A light-gated regulation of the reaction site by a cucurbit[7]uril macrocycle

  2022cites this paper
• Interlocked Molecules in Enantioselective Catalysis

  2021cites this paper
• Using the Mechanical Bond to Tune the Performance of a Thermally Activated Delayed Fluorescence Emitter**

  2021cites this paper
• Chemically Induced Mismatch of Rings and Stations in [3]Rotaxanes

  2021cites this paper
• Control of dynamic sp3-C stereochemistry

  2021cites this paper
• Spin-labelled mechanically interlocked molecules as models for the interpretation of biradical EPR spectra

  2021cites this paper
• Mechanically Interlocked Chiral Self‐Templated [2]Catenanes from 2,6‐Bis(1,2,3‐triazol‐4‐yl)pyridine (btp) Ligands

  2021cites this paper
• Mechanical bonding activation in rotaxane-based organocatalysts

  2021cites this paper
• Diastereoselective Amplification of a Mechanically Chiral [2]Catenane

  2021cites this paper
• Stereodynamics of E/Z isomerization in rotaxanes through mechanical shuttling and covalent bond rotation

  2021cites this paper
• Same knot, longer rope: altering ligand geometry provides control over nuclearity in self-assembled trefoil knots.

  2021cites this paper
• PCage: Fluorescent Molecular Temples for Binding Sugars in Water.

  2021cites this paper
• Self-Assembly of Stimuli-Responsive [2]Rotaxanes by Amidinium Exchange

  2021cites this paper
• A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes

  2021cites this paper
• Stimuli-Responsive Chiroptical Switching.

  2021cites this paper
• Post-Synthetic Macrocyclization of Rotaxane Building Blocks.

  2021cites this paper
• Anion–π Catalysis Enabled by the Mechanical Bond

  2021cites this paper
• Mechanically axially chiral catenanes and noncanonical chiral rotaxanes

  2021cites this paper
• Simplicity in the Design, Operation, and Applications of Mechanically Interlocked Molecular Machines

  2020cites this paper
• Enantiodivergent Cyclization by Inversion of the Reactivity in Ambiphilic Molecules

  2020cites this paper
• Site-to-site peptide transport on a molecular platform using a small-molecule robotic arm

  2020cites this paper
• Cross dehydrogenative C–O coupling catalysed by a catenane-coordinated copper(i)†

  2020cites this paper
• Cyclization of interlocked fumaramides into β-lactams: experimental and computational mechanistic assessment of the key intercomponent proton transfer and the stereocontrolling active pocket

  2020cites this paper
• Mechanically Interlocked Catalysts for Asymmetric Synthesis

  2020cites this paper
• Strategies for the Synthesis of Enantiopure Mechanically Chiral Molecules

  2020cites this paper
• Supramolecular Relay-Control of Organocatalysis with a Hemithioindigo-Based Molecular Motor.

  2020cites this paper
• A Switchable Catalyst Duo for Acyl Transfer Proximity Catalysis and Regulation of Substrate Selectivity

  2020cites this paper
• Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes

  2020cites this paper
• Stereoselective Synthesis of a Topologically Chiral Solomon Link.

  2020cites this paper
• Enantiodivergent cyclization by inversion of the reactivity in ambiphilic molecules.

  2020cites this paper
• Functionalized Macrocycles in Supramolecular Organocatalysis.

  2020cites this paper
• Single-Step Enantioselective Synthesis of Mechanically Planar Chiral [2]Rotaxanes Using a Chiral Leaving Group Strategy

  2020cites this paper
• Driving Smart Molecular Systems by Artificial Molecular Machines

  2020cites this paper
• Synthesis of a Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis

  2020cites this paper
• Enhancing the selectivity of prolinamide organocatalysts using the mechanical bond in [2]rotaxanes

  2020cites this paper
• Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetrastable Donor-Acceptor [2]Rotaxane.

  2020cites this paper
• Heterobifunctional Rotaxanes for Asymmetric Catalysis

  2019cites this paper
• Stereodivergent Anion Binding Catalysis with Molecular Motors

  2019cites this paper