The cheletropic ene-reaction and its reversal; additions to 1,2,3,4-tetrachloro-5-methylenecyclohexa-1,3-diene

Grimme, Wolfram; Härter, Michael; Sklorz, Christoph A.

doi:10.1039/a901770d

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Ene Reactions1

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2003

2013

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Cited by 7 publications

(2 citation statements)

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“…Grimme, HÌrter and Sklorz present a new type of ene reaction, the cheleotropic ene (Scheme 2). 85 Although no examples of this reaction are currently known, the fragmentations of b-ketoaldehydes or b,g-unsaturated aldehydes provide examples of the retro-reaction. Decarbonylation of b,g-unsaturated aldehydes is believed to proceed via a pericyclic transition state.…”

Section: Ene Reactionsmentioning

confidence: 99%

Reaction Mechanisms. Part 2. Pericyclic Reactions

Morgan¹

2003

ChemInform

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Section: Ene Reactionsmentioning

confidence: 99%

Reaction Mechanisms. Part 2. Pericyclic Reactions

Morgan¹

2003

ChemInform

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“…There are a l s o fragmentations that can be interpreted as the reverse of this reaction. The thermal decarboxylation of β-ketoaldehydes [5] and, β,γunsaturated aldehydes and imines [6] fall in this category.…”

Section: Introductionmentioning

confidence: 98%

N-Phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine retro cheletropic-ene reaction, a theoretical kinetic study

Izadyar

2013

Progress in Reaction Kinetics and Mechanism

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Structural and kinetic aspects of the retro-cheletropic ene reactions of N-phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine (R) and its deuterated derivative were investigated using a variety of computational methods. Theoretical calculations were carried out with DFT methods at the B3LYP and M06 levels of theory, using the 6-311++G(d,p) basis set. Vibrational frequency analysis confirmed the stationary states including the transition state (TSs) structures. The mechanistic studies on the retro-cheletropic ene processes rejected the stepwise mechanism and confirmed a five-membered cyclic TS for the reaction. The conversion of the reactant to the products proceeds through an asynchronous concerted mechanism. Theoretical calculations indicate that the reaction displays a primary kinetic isotope effect of 8.75 at 417 K. Calculated activation parameters, especially M06 results, are in g o o d agreement with the experimental data. The natures of bond making and breaking during the reactions have been investigated using the concepts of donor-acceptor, electron charge density and Laplacian in NBO and AIM methods, respectively.

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Tetrachlorothiophene Dioxide

Grimme¹

2005

Encyclopedia of Reagents for Organic Synthesis

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The cheletropic ene-reaction and its reversal; additions to 1,2,3,4-tetrachloro-5-methylenecyclohexa-1,3-diene

Cited by 7 publications

References 22 publications

Reaction Mechanisms. Part 2. Pericyclic Reactions

Reaction Mechanisms. Part 2. Pericyclic Reactions

N-Phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine retro cheletropic-ene reaction, a theoretical kinetic study

Tetrachlorothiophene Dioxide

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