Dynamic Control of Chiral Space in a Catalytic Asymmetric Reaction Using a Molecular Motor

  title={Dynamic Control of Chiral Space in a Catalytic Asymmetric Reaction Using a Molecular Motor},
  author={Jiaobing Wang and Ben L. Feringa},
  pages={1429 - 1432}
Photoisomerization of a molecular catalyst changes its conformation and switches the chirality of its reaction product. Enzymes and synthetic chiral catalysts have found widespread application to produce single enantiomers, but in situ switching of the chiral preference of a catalytic system is very difficult to achieve. Here, we report on a light-driven molecular motor with integrated catalytic functions in which the stepwise change in configuration during a 360° unidirectional rotary cycle… Expand

Topics from this paper

Dynamic control of chirality in phosphine ligands for enantioselective catalysis
It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction. Expand
Enantiopure Functional Molecular Motors Obtained by a Switchable Chiral-Resolution Process.
This method provides rapid access to ample amounts of enantiopure molecular motors, which will greatly facilitate the further development of responsive molecular systems based on chiral overcrowded alkenes. Expand
Real-Time Control of the Enantioselectivity of a Supramolecular Catalyst Allows Selecting the Configuration of Consecutively Formed Stereogenic Centers.
The enantiomeric state of a supramolecular copper catalyst can be switched in situ in ca. five seconds. The dynamic property of the catalyst is provided by the non-covalent nature of the helicalExpand
Chiral Switchable Catalysts for Dynamic Control of Enantioselectivity
Among the artificial switchable catalysts, those catalysts whose activity can be switched by an external stimulus, only a few cases offer the possibility to develop an effective chiral switchableExpand
Photomechanical actuation of ligand geometry in enantioselective catalysis.
A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported, laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Expand
Heat and Light Switch a Chiral Catalyst and Its Products
  • T. Ooi
  • Chemistry, Medicine
  • Science
  • 2011
On page 1429 of this issue, Wang and Feringa introduce a conceptually new approach in which the structure of a single catalyst can be manipulated by cycles of light and heat to pulses to create two forms of the catalysts that give reaction products of opposite chirality. Expand
Central-to-Helical-to-Axial-to-Central Transfer of Chirality with a Photoresponsive Catalyst
The potential for dynamic control of axial chirality was demonstrated by using (R)-1 as switchable catalyst to direct the stereochemical outcome of the catalytic enantioselective addition of diethylzinc to aromatic aldehydes, with successful reversal of enantiOSElectivity for several substrates. Expand
Synthesis of a Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis
A mechanically planar chiral rotaxane-based Au complex that mediates a cyclopropanation reaction with stereoselectivities that are comparable with the best conventional covalent catalyst reported for this reaction are described. Expand
By-design enantioselective self-amplification based on non-covalent product-catalyst interactions.
It is shown that product interaction with chiral recognition sites attached to structurally flexible phoshoramidite-type catalysts can sense the chirality and induce enantioselectivity in the catalyst. Expand
Dynamic Inversion of Stereoselective Phosphate Binding to a Bisurea Receptor Controlled by Light and Heat.
H’NMR titrations demonstrate that the P’and M’helical cis’isomers hold opposite enantioselectivity in the binding of binol phosphate, while anion complexation by the intermediate trans isomer is not selective. Expand


Light-driven monodirectional molecular rotor
Attempts to fabricate mechanical devices on the molecular level have yielded analogues of rotors, gears, switches, shuttles, turnstiles and ratchets. Molecular motors, however, have not yet beenExpand
Enantioselective organocatalytic direct Michael addition of nitroalkanes to nitroalkenes promoted by a unique bifunctional DMAP-thiourea.
Remarkably, the asymmetric induction increases with decreasing catalyst loading with the optimal compromise between rate and induction at a loading of 2 mol %. Expand
Artificial light-gated catalyst systems.
This Review outlines the general concept of light-gated catalysis based on photocaged and also photoswitchable systems, and discusses relevant examples of the past and recent literature. Expand
Photoswitchable intramolecular H-stacking of perylenebisimide.
This approach allows for efficient control of intramolecular H-stack formation with no significant intermolecular interactions spanning over at least 4 orders of magnitude of concentration (from 10(-8) to 10(-4) M) and a range of solvents and temperatures. Expand
Highly enantioselective organocatalytic sulfa-Michael addition to alpha,beta-unsaturated ketones.
A cinchona alkaloid-derived urea was found to be an efficient organocatalyst for catalyzing enantioselective conjugate addition between thiols and various alpha,beta-unsaturated ketones to provideExpand
Modern Physical Organic Chemistry
1: Introduction to Structure and Models of Bonding 2: Strain and Stability 3: Solutions and Noncovalent Binding Forces 4: Molecular Recognition and Supramolecular Chemistry 5: Acid-Base Chemistry 6:Expand
Molecular machines: Nanomotor rotates microscale objects
A synthetic, light-driven molecular motor that is embedded in a liquid-crystal film and can rotate objects placed on the film that exceed the size of the motor molecule by a factor of 10,000. Expand
A redesign of light-driven rotary molecular motors.
This redesign of unidirectional light-driven rotary molecular motors in which the naphthalene moieties are exchanged for substituted phenyl moieties should enable the design and synthesis of more complex systems. Expand
Enantioselective Michael reaction of malonates to nitroolefins catalyzed by bifunctional organocatalysts.
Michael reaction of malonates to nitroolefins with chiral bifunctional organocatalysts, bearing both a thiourea and tertiary amino group, afforded Michael adducts with high yields andExpand
The advent and development of organocatalysis
My opinion on why the field of organocatalysis has blossomed so dramatically over the past decade is presented. Expand