2,5‐Dihydro‐1,2‐oxaphosphol‐2‐ium Ions, as Highly Reactive Phosphorus‐Centered Electrophiles: Generation, NMR Study, and Reactions

Lozovskiy, Stanislav V.; Ivanov, А. Yu.; Bogachenkov, Alexander S.

doi:10.1002/slct.201700637

Cited by 9 publications

(5 citation statements)

References 32 publications

(1 reference statement)

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“…The NMR data, including 1 H, 13 C, DEPT, COSY, and HSQC spectra (see Supporting Information File 1 ), demonstrated unambiguously that compounds 1a,b and 2a – h underwent cyclization into the corresponding ions Aa , b and Ba – h via protonation (deuteration for D 2 SO 4 , Bd- d ) of the central carbon allenic triad followed by nucleophilic attack of oxygen of the SO 2 group (for Ba – h ) or SO group (for Aa , b ) onto the carbocationic center. The similar cyclization was observed for phosphonoallenes (see P1 , P2 , Table 1 ) by us previously [ 30 , 32 ]. A new signal of the attached proton H4 at δ 8.05–6.83 ppm range appeared in 1 H NMR spectra of species A , B .…”

Section: Resultssupporting

confidence: 87%

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Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

Lozovskiy

Ivanov

Khoroshilova

et al. 2018

Beilstein J. Org. Chem.

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In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2–CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO–CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2–CR1=C–C(Me)=CH2, for R2 = R3 = Me, yields of 87–98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)–HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3, yields of 78–99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-dioxides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.

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Section: Resultssupporting

confidence: 87%

“…Based on our recent work on transformations of phosphonoallenes under the action of strong Brønsted or Lewis acids [ 29 – 32 ], we undertook a special study on reactions of (arylsulfonyl)allenes 2a – j and (arylsulfinyl)allenes 1a , b ( Scheme 1 ).…”

Section: Introductionmentioning

confidence: 99%

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

Lozovskiy

Ivanov

Khoroshilova

et al. 2018

Beilstein J. Org. Chem.

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“…This indicates that in species E2 and E4 this carbon is connected to a protonated amino group, and in E1 it is bound to oxygen. The same range of absorbance around 100 ppm for this carbon was observed previously for other oxaphospholium ions [14,16].…”

Section: Resultssupporting

confidence: 84%

Different reactivity of phosphorylallenes under the action of Brønsted or Lewis acids: a crucial role of involvement of the P=O group in intra- or intermolecular interactions at the formation of cationic intermediates

Lozovskiy¹,

Ivanov²,

Vasilyev³

2019

Beilstein J. Org. Chem.

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3-Methylbuta-1,2-dien-1-ylphosphonic acid derivatives (phosphorylallenes) [X2(O=)P–CR=C=CMe2, X = Cl, OMe, NR2, or SAr] undergo intramolecular cyclization into the corresponding 1,2-oxaphospholium ions in the Brønsted superacid TfOH. These cations have been thoroughly studied by means of NMR spectroscopy. The hydrolysis of superacidic solutions of these species afforded cyclic phosphonic acids and other phosphorus-containing compounds. Contrary to Brønsted acids, 3-methylbuta-1,2-dien-1-ylphosphonic dichloride [Cl2(O=)P–HC=C=CMe2] reacted with the Lewis acid AlCl3 in an intermolecular way forming noncyclic intermediates, which were investigated by NMR spectroscopy and DFT calculations. Hydrolysis of these species resulted in the formation of phosphoryl-substituted allyl alcohols and 1,3-butadienes. A strong coordination of the oxygen of the P=O group with AlCl3 prevented the formation of cyclic 1,2-oxaphospholium ions and played a crucial role in the different reactivity of such phosphorylallenes under the action of Brønsted or Lewis acids. Apart from that, the reaction of dichlorophosphorylallenes with arenes and AlCl3 led to products of hydroarylation of the allene system, phosphoryl-substituted alkenes and/or indanes. This is the first example of a Lewis acid-promoted intermolecular hydroarylation of allenes bearing electron-withdrawing substituents. Plausible reaction mechanisms have been proposed on the basis of the investigated reactions, and NMR analysis and DFT studies of the intermediate cationic species.

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“… Some examples of common superelectrophilic species [ 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ] ( A ), the reactions of organophosphorus superelectrophiles reported thus far [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ] ( B ), the known arylation of phosphacoumarins ( C ) and the superelectrophilic activation of phosphacoumarins reported in this work ( D ). …”

Section: Figure and Schemesmentioning

confidence: 94%

“…The reactions of vinyl type carbocations derived from ethynylphosphonates with substituted benzenes in fluorosulfonic acid have been described by Vasil’ev and coworkers [ 21 , 22 ]. Later, the same group reported a series of transformations of 1-(phosphoryl)allenes in superacidic media, which furnished various phosphorus heterocycles [ 23 , 24 , 25 , 26 , 27 ]. Thus far, these are the only known reactions of organophosphorus superelectrophiles.…”

Section: Introductionmentioning

confidence: 99%

Superelectrophilic Activation of Phosphacoumarins towards Weak Nucleophiles via Brønsted Acid Assisted Brønsted Acid Catalysis

Zalaltdinova,

Sadykova,

Gazizov

et al. 2024

IJMS

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The electrophilic activation of various substrates via double or even triple protonation in superacidic media enables reactions with extremely weak nucleophiles. Despite the significant progress in this area, the utility of organophosphorus compounds as superelectrophiles still remains limited. Additionally, the most common superacids require a special care due to their high toxicity, exceptional corrosiveness and moisture sensitivity. Herein, we report the first successful application of the “Brønsted acid assisted Brønsted acid” concept for the superelectrophilic activation of 2-hydroxybenzo[e][1,2]oxaphosphinine 2-oxides (phosphacoumarins). The pivotal role is attributed to the tendency of the phosphoryl moiety to form hydrogen-bonded complexes, which enables the formation of dicationic species and increases the electrophilicity of the phosphacoumarin. This unmasks the reactivity of phosphacoumarins towards non-activated aromatics, while requiring only relatively non-benign trifluoroacetic acid as the reaction medium.

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2,5‐Dihydro‐1,2‐oxaphosphol‐2‐ium Ions, as Highly Reactive Phosphorus‐Centered Electrophiles: Generation, NMR Study, and Reactions

Cited by 9 publications

References 32 publications

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

Different reactivity of phosphorylallenes under the action of Brønsted or Lewis acids: a crucial role of involvement of the P=O group in intra- or intermolecular interactions at the formation of cationic intermediates

Superelectrophilic Activation of Phosphacoumarins towards Weak Nucleophiles via Brønsted Acid Assisted Brønsted Acid Catalysis

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