1,3-hydrogen shift in phosphapropenes. Suprafacial sigmatropic rearrangements

Nguyen, Minh Tho; Landuyt, Luc; Vanquickenborne, L. G.

doi:10.1016/0009-2614(93)87242-u

Cited by 12 publications

(6 citation statements)

References 12 publications

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“…[41] This thermal isomerization has been studied from a theoretical standpoint. [42] Unlike the corresponding allcarbon systems, a concerted suprafacial [1,3] sigmatropic shift of the hydrogen atom seems to be possible.…”

Section: F Matheymentioning

confidence: 91%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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Section: F Matheymentioning

confidence: 91%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…(12) ] 41. Einer theoretischen Untersuchung42 dieser thermischen Isomerisierung zufolge kann anders als bei den analogen reinen Kohlenstoffverbindungen eine konzertierte suprafaciale [1,3]‐sigmatrope Verschiebung des Wasserstoffatoms stattfinden.…”

Section: Phosphaalkeneunclassified

Phosphaorganische Chemie: Panorama und Perspektiven

Mathey

2003

Angewandte Chemie

198

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Die gesamte phosphororganische Chemie wurde mit Beginn der siebziger Jahre infolge der Entdeckung stabiler phosphororganischer Derivate mit Koordinationszahlen des Phosphors von 1 oder 2 aufgefrischt. Bezüglich ihrer Chemie gleichen diese Verbindungen ihren reinen Kohlenstoff‐Analoga. Dieser Aufsatz widmet sich der Analogie zwischen den Phosphorderivaten und den entsprechenden Alkenen, Alkinen und Carbenen, wobei jede Verbindungsklasse anhand ihrer Synthese, ihrer Reaktivität und ihres Koordinationstyps kurz vorgestellt wird. Des Weiteren werden besondere Elektronenkonfigurationen der Phosphorverbindungen behandelt, darunter P‐P‐Einelektronenbindungen, gespannte Bindungen und aromatische Systeme. Abschließend wird auf mögliche Anwendungen dieser Chemie zur Herstellung molekularer Materialien und in der homogenen Katalyse verwiesen.

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“…Although there is no definitive experimental evidence for a thermal, concerted [1,3]hydrogen shift in a hydrocarbon system, this possibility has been already pointed out for related systems such as alkyl-substituted allenes, 1-silapropene, and 1-phosphapropene. [10][11][12][13][14] The benchmark [1 s ,3 a ] rearrangement of hydrogen in the allyl system (propene) has been extensively studied from a theoretical viewpoint. [15][16][17][18][19][20][21][22][23][24] The interest has been mainly devoted to the elucidation and understanding of structural, dynamical, and thermodynamical aspects of such fundamental pericyclic chemical processes.…”

Section: Introductionmentioning

confidence: 99%

“…Particularly interesting are the unimolecular and one step [1,3] sigmatropic rearrangements because of their relevant applications in organic and inorganic synthetic chemistry. Although there is no definitive experimental evidence for a thermal, concerted [1,3]hydrogen shift in a hydrocarbon system, this possibility has been already pointed out for related systems such as alkyl-substituted allenes, 1-silapropene, and 1-phosphapropene. − The benchmark [1 s ,3 a ] rearrangement of hydrogen in the allyl system (propene) has been extensively studied from a theoretical viewpoint. − The interest has been mainly devoted to the elucidation and understanding of structural, dynamical, and thermodynamical aspects of such fundamental pericyclic chemical processes. Results, based on several types of calculations, have been finally interpreted in terms of the simple theoretical principles of the Woodward−Hoffmann rules for the conservation of orbital symmetry.…”

Section: Introductionmentioning

confidence: 99%

The Bonding Nature of Some Simple Sigmatropic Transition States from the Topological Analysis of the Electron Localization Function

et al. 2002

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It is shown that the topological analysis of the electron localization function (ELF), a measure of the local Pauli repulsion, is a useful tool to describe the bonding nature of transition structures of simple pericyclic processes. In this work, we have revisited the [1s,3a]hydrogen, [1a,3s]methyl, and [1a,3s]fluorine simple sigmatropic rearrangements in the allyl system. Results based on the integrated densities over the ELF basins and their related properties at the B3LYP/6-311++G(d,p) level of theory showed explicitly a delocalized structure for the antarafacial (Cs) hydrogen rearrangement, a two radical interaction for the methyl suprafacial (C2) migration, and a pair−ion interaction for the fluorine suprafacial (Cs) transfer. Results on these well-studied systems confirm the topological analysis of the ELF as a useful descriptor for the study of bonding structure of pericyclic transition states. In this context, the ELF analysis is shown to be a complementary value to the Woodward−Hoffmann rules, which provide an orbital symmetry basis of understanding.

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1,3-hydrogen shift in phosphapropenes. Suprafacial sigmatropic rearrangements

Cited by 12 publications

References 12 publications

Phospha‐Organic Chemistry: Panorama and Perspectives

Phospha‐Organic Chemistry: Panorama and Perspectives

Phosphaorganische Chemie: Panorama und Perspektiven

The Bonding Nature of Some Simple Sigmatropic Transition States from the Topological Analysis of the Electron Localization Function

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