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

@article{Wang2011DynamicCO,
  title={Dynamic Control of Chiral Space in a Catalytic Asymmetric Reaction Using a Molecular Motor},
  author={Jiaobing Wang and Ben L. Feringa},
  journal={Science},
  year={2011},
  volume={331},
  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

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References

SHOWING 1-10 OF 30 REFERENCES
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.
TLDR
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.
TLDR
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.
TLDR
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
TLDR
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.
TLDR
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
TLDR
My opinion on why the field of organocatalysis has blossomed so dramatically over the past decade is presented. Expand
...
1
2
3
...