Valence tautomerism in cis-2-vinylcyclopropanecarboxaldehyde. 2,5-Dihydrooxepin

Rhoads, Sara Jane; Cockroft, Robert D.

doi:10.1021/ja01038a087

Cited by 52 publications

(32 citation statements)

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“…22 Such a [3,3]-sigmatropic reaction was previously thought to be concerted and undergo a six-member-ring transition state. Considering that the most commonly used RCs in earlier studies of Claisen rearrangement 29 are the C1–C6 ( d (C1–C6), Figure 1B) and/or O3–C4 ( d (O3–C4) bond length(s) (Supporting Information, Figure S3), we first calculated the free-energy profiles along these dimensions.…”

Section: Resultsmentioning

confidence: 99%

Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories

Zhang

Yang

et al. 2017

ACS Cent. Sci.

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Efficient sampling in both configuration and trajectory spaces, combined with mechanism analyses via data mining, allows a systematic investigation of the thermodynamics, kinetics, and molecular-detailed dynamics of chemical reactions in solution. Through a Bayesian learning algorithm, the reaction coordinate(s) of a (retro-)Claisen rearrangement in bulk water was variationally optimized. The bond formation/breakage was found to couple with intramolecular charge separation and dipole change, and significant dynamic solvent effects manifest, leading to the “in-water” acceleration of Claisen rearrangement. In addition, the vibrational modes of the reactant and the solvation states are significantly coupled to the reaction dynamics, leading to heterogeneous and oscillatory reaction paths. The calculated reaction rate is well interpreted by the Kramers’ theory with a diffusion term accounting for solvent–solute interactions. These findings demonstrated that the reaction mechanisms can be complicated in homogeneous solutions since the solvent–solute interactions can profoundly influence the reaction dynamics and the energy transfer process.

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Section: Resultsmentioning

confidence: 99%

Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories

Zhang

Yang

et al. 2017

ACS Cent. Sci.

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“…The activation enthalpy for the Cope rearrangement in the boat transition state (X = H,H) has been estimated as 41 kcal/mole, whereas the corresponding cyclopropyl case (X = C H 2) has an activation enthalpy of about 21 kcal/mole (Doering et al, 1968). Also compatible with this rationale is the great acceleration provided the X = C H 2 case when an oxygen replaces one of the vinyl terminal C H 2 groups (Rhoads and Cockcroft, 1969) and the increased activation energy for the X = C H 2 case as the vinyl groups are alkylated (Pickenhagen et al, 1973). The qualitative rates of rearrangement of the heteroanalogs (X = C H 2 > N H » 0 > S; Paquette and Haluska, 1970) can be attributed to the varying donor abilities of the Walsh-type occupied orbitals of these molecules (Moliere and Houk, 1977).…”

Section: Reactivitymentioning

confidence: 99%

“…Among the notable examples of reactions in which [2 + 2] and [4 + 2] cycloadditions compete effectively are numerous cycloadditions of haloalkenes to dienes(Roberts and Sharts, 1962; Only a few of the known examples will be discussed here.The best known examples of stepwise Diels-Alder reactions involve either nonpolar partners or highly unsymmetrical polar partners.…”

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confidence: 99%

Applications of Frontier Molecular Orbital Theory to Pericyclic Reactions

Houk¹

1977

Organic Chemistry: A Series of Monographs

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“…Whereas, however, the 8a+9a equilibrium is 19:l in favor of the cyclopropane [ 5 ] , the coulombic repulsion of the a-dicarbonyl system of cyclopropane 8b may be responsible for the dislocation of the 8b+9b equilibrium in favor of the dihydrooxepine. trunslcis-Isomerization of ketone 5 (i. e. 5+8b conversion) on photolysis [6] led to dihydrooxepinecarboxylate 6 ( = 9b in 80% yield).…”

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confidence: 98%

“…On the assumption of the last two facts being interconnected, a simple explanation emerges. In analogy with the valence tautomerism of cis-2-vinylcyclopropanecarboxaldehyde (8a) and 2,5-dihydrooxepine (9a) [5], the unob-…”

mentioning

confidence: 99%

The Reaction of 1,3‐Butadiene with Ethyl Diazopyruvate. Syntheses of Salicylates and of Nezukone

Wenkert

Greenberg

Kim

1987

Helvetica Chimica Acta

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The Rh-catalyzed reaction of 1,3-butadiene with ethyl 3-diazopyruvate leads, inter atia, to a dihydrooxepinecarboxylate whose oxidation and functional-group manipulation produce salicylates. Wittig reactions on the acylcyclopropane accompanying the dihydrooxepine yields acrylates whose pyrolyses afford cycloheptadienecarboxykdtes. Oxidation and functional-group transformation produces the natural tropone, nezukone.Introduction. -Whereas CI -diazocarbonyl compounds are transformed normally into acylcyclopropanes on metal-assisted decomposition in the presence of olefins, diazopyruvates, e.g. 1, are converted into 4,5-dihydro-2-furoates in this reaction with electrynrich olefins as, for example, enol ethers [l]'). In the case of the reaction of ethyl diazopyruvate (1) with a conjugated dienol ether, the dihydrofuroate product was accompanied by a dihydrooxepine derivative [le]. In order to ascertain the sequence of events responsible for this unusual result, a study of the reaction of ethyl diazopyruvate (1) with a simpler diene, i.e. 1,3-butadiene (2), was undertaken.

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Valence tautomerism in cis-2-vinylcyclopropanecarboxaldehyde. 2,5-Dihydrooxepin

Cited by 52 publications

References 0 publications

Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories

Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories

Applications of Frontier Molecular Orbital Theory to Pericyclic Reactions

The Reaction of 1,3‐Butadiene with Ethyl Diazopyruvate. Syntheses of Salicylates and of Nezukone

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