Linear analysis of labeling experiments. Application to sigmatropic rearrangements of 1,5-hexadiene

Goldstein, M. J.; Benzon, M. S.

doi:10.1021/ja00775a047

Cited by 14 publications

(7 citation statements)

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“…Caled for Ci2H20: C, 88.82; H, 11.18. Found: C, 88.91; H, 11.16. l,2-Di(l-cyclohexenyl)ethane (5). In a pyrolysis identical with the above 2,2'-bismethylenecyclohexane after 1 h at 300 °C gave >99% compound 5.…”

Section: Methodsmentioning

confidence: 68%

“…By analogy with the known and carefully investigated conformations of cyclohexane,4 the chair and boat forms were considered to be two likely possibilities, although 7 /::y -1 a more thorough mechanistic analysis has revealed several alternative transition-state geometries for these rearrangements. [5][6][7] This added complexity has not altered the impact of the classic investigation of Doering and Roth which established the chair-like transition state as the lowest energy reaction pathway.8 In an overwhelming majority of cases, the stereochemical outcome of [3.3] sigmatropic rearrangement of substituted derivatives of l ,5-dienes is best understood in terms of a chair-like conformation. Substituents orient themselves so that the bulkiest prefer to occupy the less congested quasi-equatorial positions.9 This arrangement also usually gives rise to the thermodynamically most stable E isomer.…”

Section: Introductionmentioning

confidence: 99%

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Diastereomeric transition states. Relative energies of the chair and boat reaction pathways in the Cope rearrangement

Shea¹,

Phillips²

1980

J. Am. Chem. Soc.

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Section: Methodsmentioning

confidence: 68%

Section: Introductionmentioning

confidence: 99%

Diastereomeric transition states. Relative energies of the chair and boat reaction pathways in the Cope rearrangement

Shea¹,

Phillips²

1980

J. Am. Chem. Soc.

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“…In the present context, the allowed changes would generate a subgroup of G128 and the orbital isomers would be analogous to possible residual stereoisomers in the tetraphenylethane even though the reason for the existence of the energy barriers is different. A kinetic study of labeled 1,5-hexadienes has been done (24).…”

Section: P Gmentioning

confidence: 99%

An Algebraic Description of Stereochemical Correspondence

Nourse

1975

Proc. Natl. Acad. Sci. U.S.A.

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It is shown that a stereochemical correspondence between two molecular systems can be represented by a commuting diagram of the point groups and permutation groups involved. The effect of the diagrammatic condition on the mappings of the cosets, double cosets, subgroup lattice, and double coset algebra determined for the two molecular systems by point group to permutation group homomorphisms is detailed. Chemical similarities implied by a stereochemical correspondence are indicated, and six examples are provided and discussed.

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“…(3) and (59) that these normal coordinates are obtained as linear combinations of the deviations 5; of the molal ratios m; from their values in the final equilibrium state. Symmetry considerations can occasionally be used to simplify the above diagonalization process [17]. In such cases, rate equations having appropriate symmetries can be written down a~linear combinations of the rate equations (20) or (25); since each set of such rate equations, belonging to a particular symmetry group, can be treated separately, the original diagonalization problem is broken down into a number of simpler problems.…”

Section: Normal Coordinates As Linear Combinations Of Deviations Frommentioning

confidence: 99%

Matrix Methods and Normalization Procedures in Chemical Relaxation

Hayman

1973

Israel Journal of Chemistry

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Two very general methods for dealing with chemical relaxation in solution near equilibrium are developed in detail along parallel lines; in the first of these the normal modes of relaxation are obtained as linear combinations of a set of basic reactions whereas in the second the normal coordinates are obtained as linear combinations of the deviations of the solute concentrations from those at equilibrium. The general procedures described in the literature, differing both in their basic assumptions (some being based on the theory of irreversible thermodynamics, others on kinetic considerations) and also in the concentration units adopted and the normalization procedures used, form special cases of the above two general methods and are considered from this point of view. The two general methods are compared critically and shown to be complementary since each has its own special advantages and disadvantages. In particular, the significance of the normal modes of relaxation corresponding to infinite relaxation times are shown to be entirely different in the two cases; in the first method these modes are “reactionless” and have little significance whereas the “improper” normal modes obtained by the second method show how the concentrations of the various solutes can be changed without disturbing the chemical equilibrium of the system.

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Linear analysis of labeling experiments. Application to sigmatropic rearrangements of 1,5-hexadiene

Cited by 14 publications

References 1 publication

Diastereomeric transition states. Relative energies of the chair and boat reaction pathways in the Cope rearrangement

Diastereomeric transition states. Relative energies of the chair and boat reaction pathways in the Cope rearrangement

An Algebraic Description of Stereochemical Correspondence

Matrix Methods and Normalization Procedures in Chemical Relaxation

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