Aryl group – a leaving group in arylphosphine oxides

Stankevič, M.; Pisklak, Jolanta; Włodarczyk, Katarzyna

doi:10.1016/j.tet.2015.12.043

Cited by 28 publications

(32 citation statements)

References 62 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%

“…For substrates 6-25, the 31 P NMR shifts were in the range of 32.66-39.33 ppm, which was the typical range for aryldialkylphosphine sulfides [70,71]. The signal of aryldialkylphosphine oxides are usually found around 30-50 ppm [61,72,73], and hence the overlapping signals make this technique inappropriate for the analysis of the reaction products.…”

Section: Methodsmentioning

confidence: 99%

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[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%

Section: Methodsmentioning

confidence: 99%

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

Włodarczyk

Borowski

Stankevič

2020

Beilstein J. Org. Chem.

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“…al. [68] However, when phenyl-3-phospholene oxide was heated in the presence of 1 equiv of Cs 2 CO 3 in toluene, the crude product obtained after the reaction contained the mixture of 1-phenyl-2-phospholene oxide 4a and the corresponding 3-phospholene oxide 1a in a 77:23 ratio. Based on this promising preliminary result, 1-ethyl-3-methyl-3-phospholene oxide (1h) was also included as a model compound for the alkyl derivatives.…”

Section: Investigation Of the Isomerization Of 3-phospholene Oxides 1mentioning

confidence: 99%

Preparation of 2-phospholene oxides by the isomerization of 3-phospholene oxides

Bagi¹,

Herbay²,

Péczka³

et al. 2020

Beilstein J. Org. Chem.

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A series of 1-substituted-3-methyl-2-phospholene oxides was prepared from the corresponding 3-phospholene oxides by double bond rearrangement. The 2-phospholene oxides could be obtained by heating the 3-phospholene oxides in methanesulfonic acid, or via the formation of cyclic chlorophosphonium salts. Whereas mixtures of the 2- and 3-phospholene oxides formed, when the isomerization of 3-phospholene oxides was attempted under thermal conditions, or in the presence of a base. The mechanisms of the various double bond migration pathways were elucidated by quantum chemical calculations.

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“…In this reaction, the oxygen atom of the phosphoryl group rst reacted with triic anhydride Tf 2 O to generate an electrophilic intermediate and this was followed by electrophilic aromatic ring closure enhanced by the electron-releasing hydroxyl group; nal OH/OTf conversion afforded 154 in 35% yield (Scheme 30 Stankevič et al synthesised a new group of bulky 5-tertbutyldibenzophosphole 5-oxides from acyclic diaryl-tert-butylphosphine oxides and organolithiums. 43 Other syntheses of dibenzophospholes starting from phosphine oxides of type ArR 2 P(O) and R 3 P(O) are described in the subsection 2.7. Synthesis of dibenzophospholes from aryl substituted phosphine oxides Ar 3 P(O) and ArR 2 P(O) has been described in the previous subsection 2.6.…”

Section: From Ar 3 P(o) or Arr 2 P(o)mentioning

confidence: 99%