QM/MM Protocol for Direct Molecular Dynamics of Chemical Reactions in Solution: The Water-Accelerated Diels–Alder Reaction

2015 ◽  
Vol 11 (12) ◽  
pp. 5606-5612 ◽  
Author(s):  
Zhongyue Yang ◽  
Charles Doubleday ◽  
K. N. Houk
Keyword(s):  
Molecular Dynamics ◽  
Chemical Reactions ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

QM/QM′ Direct Molecular Dynamics of Water-Accelerated Diels–Alder Reaction

2016 ◽  
Vol 120 (26) ◽  
pp. 6250-6254 ◽  
Author(s):  
Fengjiao Liu ◽  
Zhongyue Yang ◽  
Ye Mei ◽  
K. N. Houk
Keyword(s):  
Molecular Dynamics ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Boosted molecular mobility during common chemical reactions

Science ◽  
2020 ◽  
Vol 369 (6503) ◽  
pp. 537-541 ◽  
Author(s):  
Huan Wang ◽  
Myeonggon Park ◽  
Ruoyu Dong ◽  
Junyoung Kim ◽  
Yoon-Kyoung Cho ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Alder Reaction ◽  
Diels Alder ◽  
Brownian Diffusion ◽  
Organic Chemical ◽  
Sonogashira Coupling ◽  
Substitution Reactions ◽  
Bimolecular Reactions ◽  
Diels Alder Reaction ◽  
Instrumental Resolution

Mobility of reactants and nearby solvent is more rapid than Brownian diffusion during several common chemical reactions when the energy release rate exceeds a threshold. Screening a family of 15 organic chemical reactions, we demonstrate the largest boost for catalyzed bimolecular reactions, click chemistry, ring-opening metathesis polymerization, and Sonogashira coupling. Boosted diffusion is also observed but to lesser extent for the uncatalyzed Diels-Alder reaction, but not for substitution reactions SN1 and SN2 within instrumental resolution. Diffusion coefficient increases as measured by pulsed-field gradient nuclear magnetic resonance, whereas in microfluidics experiments, molecules in reaction gradients migrate “uphill” in the direction of lesser diffusivity. This microscopic consumption of energy by chemical reactions transduced into mechanical motion presents a form of active matter.

Effect of solvent motions on the dynamics of the Diels-Alder reaction

2021 ◽  
Author(s):  
Xiaoyong Zhang ◽  
Pierre-louis Lefebvre ◽  
Jeremy Harvey
Keyword(s):  
Chemical Reactions ◽  
Shape Change ◽  
Alder Reaction ◽  
Diels Alder ◽  
Effect Of Solvent ◽  
Diels Alder Reaction

How solvent motions affects the dynamics of chemical reactions in which the solute undergoes a substantial shape change is a fundamental but elusive issue. This work utilizes reactive simulation and...

The Diels-Alder Reaction of 2-Ethenyl-1,4-Benzodioxin: A New and Simple Synthesis of Bisaryl Ethers

Synlett ◽  
1989 ◽  
Vol 1989 (01) ◽  
pp. 30-32
Author(s):  
Thomas V. Lee ◽  
Alistair J. Leigh ◽  
Christopher B. Chapleo
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Simple Synthesis ◽  
Diels Alder Reaction

The intermolecular anthracene-transfer in a regiospecific antipodal C60 difunctionalization

2020 ◽  
Author(s):  
Radu Talmazan ◽  
Klaus R. Liedl ◽  
Bernhard Kräutler ◽  
Maren Podewitz
Keyword(s):  
Noncovalent Interactions ◽  
Interaction Model ◽  
Alder Reaction ◽  
Diels Alder ◽  
Stacking Interactions ◽  
Pi Stacking ◽  
Diels Alder Reaction ◽  
Double Decker ◽  
Anthracene Molecule ◽  
New Strategies

We analyze the mechanism of the topochemically controlled difunctionalization of C60 and anthracene, where an anthracene molecule is transferred from one C60 monoadduct to another one under exclusive formation of equal amounts of C60 and the difficult to make antipodal C60 bisadduct. Our herein disclosed dispersion corrected DFT studies show the anthracene transfer to take place in a synchronous retro Diels-Alder/Diels-Alder reaction: an anthracene molecule dissociates from one fullerene under formation of an intermediate, while already undergoing stabilizing interactions with both neighboring fullerenes, facilitating the reaction kinetically. In the intermediate, a planar anthracene molecule is sandwiched between two neighboring fullerenes and forms equally strong "double-decker" type pi-pi stacking interactions with both of these fullerenes. Analysis with the distorsion interaction model shows that the anthracene unit of the intermediate is almost planar with minimal distorsions. This analysis sheds light on the existence of noncovalent interactions engaging both faces of a planar polyunsaturated ring and two convex fullerene surfaces in an unprecedented 'inverted sandwich' structure. Hence, it sheds light on new strategies to design functional fullerene based materials.<br>

Natural Products Biosynthesis Involving a Putative Diels-Alder Reaction

2016 ◽  
Vol 20 (22) ◽  
pp. 2421-2442 ◽  
Author(s):  
Kévin Cottet ◽  
Maria Kolympadi ◽  
Dean Markovic ◽  
Marie-Christine Lallemand
Keyword(s):  
Natural Products ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction
Sign in / Sign up

Export Citation Format

Share Document