Facile syntheses and interconversions between simple phosphiranium and phosphirenium salts

Hockless, David C. R.; McDonald, Mark A.; Pabel, Michael; Wild, S. Bruce

doi:10.1016/s0022-328x(96)06641-7

Cited by 51 publications

(35 citation statements)

References 22 publications

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“…In addition, signals of methyl groups attached to phosphorus could be found at 1.70 and 1.71 ppm, respectively, which was in accordance with the shifts of this group in other phosphine oxides [61][62][63]. Moreover, the two signals at 2.91-2.98 and 3.16-3.24 ppm, respectively, corresponded to a hydrogen atom bonded to a sulfur atom [64,65].…”

Section: Methodssupporting

confidence: 80%

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

Włodarczyk

Borowski

Stankevič

2020

Beilstein J. Org. Chem.

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β-Hydroxyalkylphosphine sulfides undergo [1,3]- or [1,4]-sulfur atom phosphorus-to-carbon migration in the presence of Lewis or Brønsted acids. The direction of sulfur atom migration depends on the type of acid used for the reaction. In the presence of a Brønsted acid, mainly [1,3]-rearrangement is observed, whereas a Lewis acid catalyzes the [1,4]-sulfur migration. To gain insight into the mechanism of these transformations, the stereochemistry of these rearrangements have been tested, along with the conduction of some control experiments and DFT calculations.

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Section: Methodssupporting

confidence: 80%

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

Włodarczyk

Borowski

Stankevič

2020

Beilstein J. Org. Chem.

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“…[10] A novel reaction of the analogous three-membered phosphorus heterocyclic ions was recently reported, wherein the reaction of the phosphiranium salt 3 with dimethylacetylene cleanly gave the phosphirenium salt 4 by displacement of ethylene. [11] It was subsequently found that 4 reacted with a variety of alkynes to give thermodynamic mixtures of phosphirenium salts. [12] The behavior of 3 and 4 towards alkynes is reminiscent of p-ligand exchange in organometallic chemistry, and it is tempting to consider these salts as pcomplexes of the six-electron methylphenylphosphenium ion and to refer to the novel reaction as p-ligand exchange.…”

Section: Introductionmentioning

confidence: 99%

Are Pi-Ligand Exchange Reactions of Thiirenium and Thiiranium Ions Feasible? An Ab Initio Investigation

Sølling¹,

Wild²,

Radom³

1999

Chem. Eur. J.

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Ab initio calculations at the G2 level have been employed to investigate the hitherto unobserved p-ligand exchange reactions of thiirenium and thiiranium ions. Two pathways for exchange and one pathway for insertion are presented. The lower energy exchange pathway has barriers of 19.8 ± 46.6 kJ mol À1. The barriers for the second exchange pathway and for the insertion reaction are considerably larger. The calculations predict that p-ligand exchange is indeed feasible for thiirenium and thiiranium ions, that the exchange reaction is stereospecific with respect to the configuration at sulfur, and that insertion will not compete with exchange despite a high thermodynamic driving force for the former. These conclusions closely parallel those reached in a recent theoretical investigation of the corresponding phosphorus systems for which p-ligand exchange was observed experimentally.

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“…The 31 P NMR spectrum of [6 a]OTf exhibits a single high-field resonance (d = À86.3 ppm) characteristic of a phosphirenium compound. [33][34][35][36] Crystals of [6 a]OTf obtained from the reaction mixture were analyzed by X-ray crystallography and the molecular structure is depicted in Figure 7. .…”

Section: 3-diphosphetanium Cationsmentioning

confidence: 99%

PC Bonds as Building Blocks for Three‐ and Four‐Membered Heterocyclic Cations: Synthesis, Structures and Mechanistic Studies

Bates

Gates

2012

Chemistry A European J

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The activation of the P=C bond of phosphaalkenes with electrophiles is investigated as a means to prepare and characterize unusual organophosphorus compounds. Treatment of RP=CHtBu (1a: R=tBu; 1b: R=1-adamantyl) with HOTf (0.5 equiv) affords diphosphiranium salts [RP-CHtBu-PR (CH(2)tBu)]OTf ([2a]OTf and [2b]OTf), each containing a three-membered P(2)C ring. In contrast, the addition of MeOTf (0.5 equiv) to either 1a or 1b affords diphosphetanium salts [RP-CHtBu-P(Me)R-CHtBu]OTf ([3a]OTf and [3b]OTf) containing four-membered P(2)C(2) heterocycles. The phosphenium triflate [tBuP(CH(2)tBu)]OTf ([5a]OTf) and methylenephosphonium triflate [tBu(Me)P=CHtBu]OTf ([7a]OTf) are identified spectroscopically as intermediates in the formation of [2a](+) and [3a](+), respectively. The phosphenium triflate intermediate can be trapped with 2-butyne to afford phosphirenium salt [MeC=CMe-tBuPCH(2)tBu]OTf ([6a]OTf). Treatment of diphosphetanium [3a]OTf with an excess MeOTf affords [Me(2)P-CHtBu-PMetBu-CHtBu](OTf)(2) ([4a](OTf)(2)), a compound containing a diphosphetanium dication. The molecular structures are reported for [2a]OTf, [2b][H(OTf)(2)], [3a]I, [3b]I, [4a](OTf)(2), and [6a]OTf.

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Facile syntheses and interconversions between simple phosphiranium and phosphirenium salts

Cited by 51 publications

References 22 publications

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

Are Pi-Ligand Exchange Reactions of Thiirenium and Thiiranium Ions Feasible? An Ab Initio Investigation

PC Bonds as Building Blocks for Three‐ and Four‐Membered Heterocyclic Cations: Synthesis, Structures and Mechanistic Studies

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