Stereogenic Phosphorus

Engel, R.; Rizzo, J. I.

doi:10.2174/138527206778992707

Cited by 16 publications

(7 citation statements)

References 130 publications

(204 reference statements)

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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%

“…As found in references dealing with Berry's pseudorotation [10,20], the conventional interpretation of Berry's pseudorotation has implicitly presumed that all ligands on a trigonal bipyramidal skeleton are achiral when detached (or simply to be atoms). As a result, a pair of starting configurations in the two processes of Berry's pseudorotation (Fig.…”

Section: Problematic Situations Of the Conventional Interpretation Ofmentioning

confidence: 99%

“…Representative mechanisms are Berry's pseudorotation [1], Muetterties' mechanisms [2,3], and Ugi's turnstile rotation [4], as described in books [5,6] and reviews [7][8][9][10][11]. 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.…”

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: Problematic Situations Of the Conventional Interpretation Ofmentioning

confidence: 99%

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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“…In some cases an unusual effect was observed, namely that a mixture of two diastereomers differing only in the absolute configuration at phosphorus is more effective than either of the two respective homocombinations. The interesting area of ligands having stereogenic centers at phosphorus [105] has not been explored systematically in the present context. …”

Section: Angewandte Chemiementioning

confidence: 99%

Combinatorial Transition‐Metal Catalysis: Mixing Monodentate Ligands to Control Enantio‐, Diastereo‐, and Regioselectivity

Reetz

2008

Angew Chem Int Ed

245

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This review focuses on a new approach to combinatorial homogeneous transition-metal catalysis which goes beyond the traditional parallel preparation of modular ligands. It is based on the use of mixtures of monodentate ligands L(a) and L(b), which upon exposure to a transition metal (M) form not only the two homocombinations [ML(a)L(a)] and [ML(b)L(b)], but also the heterocombination [ML(a)L(b)]. If the latter is more reactive and selective than the homocombinations, an improved catalyst system is formed without the need to synthesize new ligands. Thus, the control of enantio,- diastereo-, and regioselectivity is possible.

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“…To remedy this feature of C/A-descriptors, the term "stereogenicity" has been introduced as found in the title "Stereogenic Phosphorus" of a review on trigonal bipyramidal phosphorus compounds and so on [6]. According to the coinage of the term "stereogenicity" or "stereogenic center" (cf.…”

mentioning

confidence: 99%

Stereoisograms of trigonal bipyramidal compounds: I. Chirality and RS-stereogenicity free from the conventional “chirality” and “stereogenicity”

Fujita¹

2012

J Math Chem

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The stereoisogram approach, which has originally been developed to rationalize organic stereochemistry (Fujita in J Org Chem ), is extended and applied to inorganic stereochemistry by using trigonal bipyramidal compounds as examples. The point group D 3h of a trigonal bipyramidal skeleton is extended into the RS-stereoisomeric group of order 24, which is considered to control a stereoisogram of the trigonal bipyramidal skeleton. Stereoisograms of trigonal bipyramidal compounds derived from the skeleton correspond to subgroups of the RS-stereoisomeric group. Thereby, they are discussed in terms of attributive terms (chirality/achirality, RS-stereogenicity/RS-astereogenicity, and sclerality/asclerality) or equivalently in terms of relational terms (enantiomeric/self-enantiomeric, RS-diastereomeric/self-RSdiastereomeric, and holantimeric/self-holantimeric), where the stereoisograms are categorized into five types (Types I-V). Among them, stereoisograms of Types I, III, and V are shown to be capable of giving C/A-descriptors because of their RS-stereogenicity (or RS-diastereomeric relationships).

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Stereogenic Phosphorus

Cited by 16 publications

References 130 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

Combinatorial Transition‐Metal Catalysis: Mixing Monodentate Ligands to Control Enantio‐, Diastereo‐, and Regioselectivity

Stereoisograms of trigonal bipyramidal compounds: I. Chirality and RS-stereogenicity free from the conventional “chirality” and “stereogenicity”

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