Topological representation of the stereochemistry of displacement reactions at phosphorus in phosphonium salts and cognate systems

DeBruin, Kenneth E.; Naumann, Kaus; Zon, Gerald; Mislow, Kurt

doi:10.1021/ja01053a024

Cited by 52 publications

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“…[16][17][18] are introduced into the PCI-CFs (Eqs. [6][7][8][9][10][11][12][13][14][15]. The resulting equations are expanded to give generating functions for the respective subgroups of SSG D 3h (Eq.…”

Section: The Partial-cycle-index (Pci) Methodsmentioning

confidence: 99%

“…A systematic geometrical analysis of the stereomutation has been investigated by Lauterbur and Ramirez [12], who have noticed the Desargues-Levi graph for the isomerization process of Berry's pseudorotation. The Desargues-Levi graph has then attracted interests of several groups of theoretical chemists [13][14][15][16]. A group-theoretical approach has been applied to trigonal bipyramidal compounds by Randić [17,18].…”

Section: Introductionmentioning

confidence: 99%

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Stereoisograms of trigonal bipyramidal compounds: II. RS-stereogenicity/RS-stereoisomerism versus stereogenicity/stereoisomerism, leading to a revised interpretation of Berry’s pseudorotation

Fujita¹

2012

J Math Chem

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The stereoisogram approach (Fujita in J Org Chem 69: 3158-3165, 2004, Tetrahedron 62:691-705, 2006, Tetrahedron 65:1581-1592) is applied to trigonal bipyramidal compounds, where chiral and achiral proligands are taken into consideration. After configurations of trigonal bipyramidal compounds are enumerated by using the partial-cycle-index method (Fujita in Symmetry and combinatorial enumeration in chemistry. Springer, Berlin, 1991), they are categorized into Type I-V cases according to the stereoisogram approach. The enumerated configurations are specified by configuration indices and C/A-descriptors, which are assigned in terms of RS-diastereomeric relationships, (not of enantiomeric relationships). The concept of a multiplet of stereoisograms is proposed to formulate the concept of ortho-stereogenicity, which is concerned with ortho-diastereomeric relationships between stereoisograms. On the other hand, the concept of stereogenicity (which has been used in the conventional stereochemistry) is redefined by starting from RS-stereogenicity and by comparing with the ortho-stereogenicity, where the stereogenicity is concerned with diastereomeric relationships between pairs of enantiomers. Berry's pseudorotation for isomerization of trigonal bipyramidal compounds is reinterpreted in order to cover more general cases in which chiral moieties along with achiral moieties (i.e., all of Type I-V cases) are taken into consideration. A modified Desargues-Levi graph is proposed to cover Type I-V cases. In addition, an adamantane-like graph is proposed to formulate Berry's pseudorotation on the basis of a multiplet of stereoisograms, where quadruplets of RS-stereoisomers occupy the nodes of the graph. Thereby, a multiplet of stereoisograms is shown to be a versatile tool to characterize stereoisomerization processes of inorganic stereochemistry in addition to those of organic stereochemistry.

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Section: The Partial-cycle-index (Pci) Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Stereoisograms of trigonal bipyramidal compounds: II. RS-stereogenicity/RS-stereoisomerism versus stereogenicity/stereoisomerism, leading to a revised interpretation of Berry’s pseudorotation

Fujita¹

2012

J Math Chem

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“…Earlier the same group proposed that pseudorotation of the intermediate phosphoranes VI, VII was responsible for predominant retention of configuration during the regiospecific ring opening The stereochemical consequences (retention or inversion) of such substitution reactions may be conveniently discussed with the aid of the Desargues-Levi graph [45], which originally was proposed by Mislow [46] for stereoisomerization of pentacoordinate phosphoranes.…”

Section: Chiral Phosphoranes As Reactive Intermediatesmentioning

confidence: 99%

“…The stereochemical consequences (retention or inversion) of such substitution reactions may be conveniently discussed with the aid of the Desargues-Levi graph [45], which originally was proposed by Mislow [46] for stereoisomerization of pentacoordinate phosphoranes.…”

Section: Chiral Phosphoranes As Reactive Intermediatesmentioning

confidence: 99%

Chiral Hypervalent, Pentacoordinated Phosphoranes

et al. 2016

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“…they all belong to the same configurational subset. Indeed, retention of configuration was experimentally demonstrated 12 by the observation that the phosphine oxide produced in the oxidation of the phosphine (Scheme IV) has the same sign and magnitude of rotation whether the reagent is hydrogen peroxide or bis(2-hydroxyethyl) disulphide.…”

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confidence: 99%

Aspects of pyramidal inversion and pseudorotation

Mislow¹

1971

Pure and Applied Chemistry

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Stereochemically non-rigid molecules may undergo a variety of conformational changes, processes which do not involve bond-making or breaking. This paper deals with features of pyramidal inversion and pseudorotation which have been studied in our laboratory, with special emphasis on compounds of the second row elements.BROADLY defined 1 , conformers are isomers resulting from atomic motions which break no bonds within a molecular framework. This definition~ less restrictive than the usual one which identifies conformers with rotamers~ enlarges the scope of conformational analysis and justifies discussion und er this heading of a diversity of intramolecular motions other than rotation about single bonds. In thi~ paper, I plan to deal with some aspects ofpyramidal inversion and pseudorotation, conformational changes (according to the above definition) which have attracted considerable attention in recent years.Pyramidal inversion is commonly encountered in compounds of the type MX 3 , in which M also bears one unshared pair of electrons and generally belongs to Groups IV to VI of the Periodic Table. Pseudorotation is most frequently associated with hypervalent 2 compounds of formula type MX 5 , in which M again belongs to Groups IV to VI. W ork in our Iabaratory has dealt largely with compounds in which the coordinating element M belongs to the second row (Figure 1 ). The energy profiles for single step inversional and pseudorotational motions are illustrated for the case of phosphorus in Figure 2. Pyramidal phosphines of formula type Pabc are converted into their enantiomers by way of a planar transition state. Trigonal-bipyramidal phosphoranes of formula type Pabcde are converted into diastereemers by way of tetragonal-pyramidal transition states 3 • We shall have more to say about the energetics of this motion in connection with work to be discussed below.Our interest in this area was stimulated by studies in the stereochemistry of nucleophilic displacements at phosphorus. We bad found that the deoxygenation of optically active acyclic phosphine oxides with hexachlorodisilane proceeds with overall inversion of configuration 4 (Scheme I), that the basecatalysed hydrolysis of ethoxyphosphonium salts derived from optically 549

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Topological representation of the stereochemistry of displacement reactions at phosphorus in phosphonium salts and cognate systems

Cited by 52 publications

References 0 publications

Stereoisograms of trigonal bipyramidal compounds: II. RS-stereogenicity/RS-stereoisomerism versus stereogenicity/stereoisomerism, leading to a revised interpretation of Berry’s pseudorotation

Stereoisograms of trigonal bipyramidal compounds: II. RS-stereogenicity/RS-stereoisomerism versus stereogenicity/stereoisomerism, leading to a revised interpretation of Berry’s pseudorotation

Chiral Hypervalent, Pentacoordinated Phosphoranes

Aspects of pyramidal inversion and pseudorotation

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