Extended Hartree—Fock (EHF) theory of chemical reactions VI: hybrid DFT and post-Hartree—Fock approaches for concerted and non-concerted transition structures of the Diels—Alder reaction

A qualitative approach for quick evaluation of the reactivity of dienes such as cyclopentadiene, furan, pyrrole, indole, and isoindole for Diels–Alder reactions was applied. As qualitative methods, the frontier molecular orbital (FMO) energy gap and the Hammond postulate through bond orders and energy of the reaction were evaluated for such dienophiles as ethylene, 1,3-dioxa-4-cyclopentene, and maleic anhydride. It was demonstrated that pyrrole and benzopyrroles are poor dienes in comparison with cyclopentadiene and furan. Because the reaction is controlled by the HOMO of the diene there are special cases when isoindole can react as a diene, while the loss of indole aromaticity in the course of the reaction precludes the cycloaddition. Geometries of transition structures and the accompanying activation energies were calculated for pyrrole, indole, and isoindole as dienes. The stereoselectivity of the reaction is discussed and compared with experimental results. Key words: benzopyrroles as dienes, Diels–Alder cycloaddition, Hammond postulate.

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Transition structures of the Diels-Alder reaction of butadiene with acrolein

The Journal of Organic Chemistry ◽

10.1021/jo00266a026 ◽

1989 ◽

Vol 54 (5) ◽

pp. 1129-1134 ◽

Cited By ~ 71

Author(s):

Richard J. Loncharich ◽

Frank K. Brown ◽

K. N. Houk

Keyword(s):

Alder Reaction ◽

Diels Alder ◽

Diels Alder Reaction ◽

Transition Structures

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ChemInform Abstract: Transition Structures of the Lewis Acid Catalyzed Diels-Alder Reaction of Butadiene with Acrolein. The Origins of Selectivity.

ChemInform ◽

10.1002/chin.199037088 ◽

1990 ◽

Vol 21 (37) ◽

Author(s):

D. M. BIRNEY ◽

K. N. HOUK

Keyword(s):

Lewis Acid ◽

Alder Reaction ◽

Diels Alder ◽

Diels Alder Reaction ◽

Transition Structures ◽

Acid Catalyzed

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Transition structures of the Lewis acid-catalyzed Diels-Alder reaction of butadiene with acrolein. The origins of selectivity

Journal of the American Chemical Society ◽

10.1021/ja00167a005 ◽

1990 ◽

Vol 112 (11) ◽

pp. 4127-4133 ◽

Cited By ~ 121

Author(s):

David M. Birney ◽

K. N. Houk

Keyword(s):

Lewis Acid ◽

Alder Reaction ◽

Diels Alder ◽

Diels Alder Reaction ◽

Transition Structures ◽

Acid Catalyzed

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Boosted molecular mobility during common chemical reactions

Science ◽

10.1126/science.aba8425 ◽

2020 ◽

Vol 369 (6503) ◽

pp. 537-541 ◽

Cited By ~ 1

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.

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

Physical Chemistry Chemical Physics ◽

10.1039/d1cp05272a ◽

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...

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