Chiral Hypervalent, Pentacoordinated Phosphoranes

Krasowska, Dorota; Chrzanowski, Jacek; Kiełbasiński, P.; Drabowicz, J.

doi:10.3390/molecules21111573

Cited by 21 publications

(14 citation statements)

References 126 publications

(148 reference statements)

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“…This was well known for silicon [12,13], but with P + , this situation has not been reported before (the Menshutkin examples stop at the quaternary salt [25][26][27]). The transformation of tetravalent phosphonium salts into pentavalent phosphoranes (right side, bottom equation) is a common reaction in phosphorus chemistry [62,63].…”

Section: Scheme 5 Back-side Attack Consistent With the Walden Inversionmentioning

confidence: 79%

“…The Menshutkin reaction converts a tertiary amine into a quaternary ammonium salt by reaction with an alkyl halide. We will slightly modify this definition to involve a type S N 2@N + reaction where the central atom is a quaternary N atom [20][21][22][23][24], and, in a further step, a quaternary P atom, S N 2@P + (Scheme 4) [25][26][27].…”

Section: Menshutkin Reactionmentioning

confidence: 99%

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The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

Alkorta

Elguero

2021

Struct Chem

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This communication gives an overview of the relationships between four reactions that although related were not always perceived as such: SN2, Walden, Finkelstein, and Menshutkin. Binary interactions (SN2 & Walden, SN2 & Menshutkin, SN2 & Finkelstein, Walden & Menshutkin, Walden & Finkelstein, Menshutkin & Finkelstein) were reported. Carbon, silicon, nitrogen, and phosphorus as central atoms and fluorides, chlorides, bromides, and iodides as lateral atoms were considered. Theoretical calculations provide Gibbs free energies that were analyzed with linear models to obtain the halide contributions. The M06-2x DFT computational method and the 6-311++G(d,p) basis set have been used for all atoms except for iodine where the effective core potential def2-TZVP basis set was used. Concerning the central atom pairs, carbon/silicon vs. nitrogen/phosphorus, we reported here for the first time that the effect of valence expansion was known for Si but not for P. Concerning the lateral halogen atoms, some empirical models including the interaction between F and I as entering and leaving groups explain the Gibbs free energies.

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Section: Scheme 5 Back-side Attack Consistent With the Walden Inversionmentioning

confidence: 79%

Section: Menshutkin Reactionmentioning

confidence: 99%

The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

Alkorta

Elguero

2021

Struct Chem

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“…Phosphoranes, pentacoordinated organophosphorus compounds, have been known to show different reactivities, such as ligand coupling, from those of phosphines and phosphonium salts . Thus, incorporation of a pentacoordinated phosphorus atom into P–B bonded compounds could show unique properties and reactivities.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, incorporation of a pentacoordinated phosphorus atom into P–B bonded compounds could show unique properties and reactivities. Only a few examples of compounds bearing a P–B bond between pentacoordinated phosphorus–tetracoordinated boron atoms have appeared in either theoretical calculations, or as a reaction intermediate in formation of a possible reduction product , . Although these compounds have promising application in the construction of new compounds containing phosphorus–boron frameworks, formation of a stable P–B bonded compound with a pentacoordinated phosphorus atom is difficult.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

et al. 2020

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The isolation and reactivities of two pentacoordinated phosphorus-tetracoordinated boron bonded compounds were explored. A highly Lewis acidic boron reagent and electron-withdrawing ligand system were required to form the pentacoordinated phosphorus state of the P-B bond. The first compound, a phosphoranyl-trihydroborate, gave a THF stabilised phosphoranyl-borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement, which involved a two-fold ring expansion, to give [ ‡] Current address:

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“…[16,[19][20][21][22] The different reactivities, such as ligand coupling, [23] from those of phosphines and phosphonium salts. [24][25][26] Thus, incorporation of a . [33] A pair of the strongly electron-withdrawing C,O-bidentate ligand (-[2-C6H4C(CF3)2O]-) [34,35] around the phosphorus atom, which has been used to stabilise many other anionic hypercoordinated phosphorus compounds, [36][37][38][39][40]…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

O'Brien¹,

Kano²,

Havare³

et al. 2020

Preprint

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The isolation and reactivities of two pentacoordinated<br>phosphorus–tetracoordinated boron bonded compounds were explored. A strong Lewis acidic boron reagent and electronwithdrawing ligand system were required to form the pentacoordinated phosphorus state of the P–B bond. The first compound, a phosphoranyl-trihydroborate, gave a THF stabilised phosphoranyl-borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement reaction, which involved a two-fold ring expansion, to give a fused bicyclic compound or it could act as a mono-hydroboration reagent. The hydroboration reactivity of the intermediate was found to be more reactive towards alkynes over alkenes with good to moderate regioselectivity towards the terminal carbon. The second compound, a phosphoranyl-triarylborate, was found to have different reactivity as it was highly stable towards acids and bases. This is thought to be due to the large bulk around the P–B bond as shown in the crystal structure.<br>

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Chiral Hypervalent, Pentacoordinated Phosphoranes

Abstract: This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

Cited by 21 publications

References 126 publications

The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

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