Air- and water-stable Lewis acids: synthesis and reactivity of P-trifluoromethyl electrophilic phosphonium cations

Fasano, Valerio; LaFortune, James H. W.; Bayne, Julia M.; Ingleson, Michael J.; Stephan, Douglas W.

doi:10.1039/c7cc09128a

Cited by 39 publications

(18 citation statements)

References 49 publications

(31 reference statements)

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“…Dicationic phosphenium ions are also accessible,e ven being active in CF bond activation chemistry. [163] Neutral phosphorous(V) species show considerable Lewis acidity,w ith PF 5 or Wittig reagents as prominente xamples. [164] However,n eutralP V LSA are unknown (PF 5 has aF IA of 398 kJ mol À1 ).…”

Section: Group 15mentioning

confidence: 99%

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Lewis Superacids: Classifications, Candidates, and Applications

Greb

2018

Chemistry A European J

229

242

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Lewis acids play a major role in all areas of chemistry. For a long time, toxic, corrosive and oxidizing SbF was considered as the strongest Lewis acid known. Lately, species significantly exceeding the Lewis acidity of SbF have been realized and were termed Lewis superacids (LSA). Prospective new candidates emerge steadily, which not only outperform SbF by their strength, but also in terms of their accessibility and ease of handling. In principle, Lewis superacids allow us to combine the outstanding activity of Brønsted superacids with the excellent selectivity of a common Lewis acid. However, the broad application of Lewis superacids in synthesis is all but popular. The present review deals with strong Lewis acids. First, it critically discusses Lewis acidity scaling methods and suggests an extended definition for Lewis superacidity. It then summarizes the properties and applications of the strongest currently known Lewis acids, indexed by the fluoride ion affinity (FIA). The supporting information contains a comprehensive list of experimentally and theoretically derived FIA data as a guide for the choice of Lewis acidic reagents/catalyst. This contribution shall encourage the search for new Lewis superacids and promote their application in non-specialized laboratories.

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Section: Group 15mentioning

confidence: 99%

“…These very strong Lewis acids have been used for catalytic hydrodefluorination reactions of fluoroalkanes . Recent progress has been made especially in the air and water stability of phosphonium ions …”

Section: Overview Of Lewis Superacidsmentioning

confidence: 99%

Lewis Superacids: Classifications, Candidates, and Applications

Greb

2018

Chemistry A European J

229

242

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“…Traditional examples of main-group Lewis acid catalysts involve group 13 and 14 elements as the central locus of reactivity,a stheyf eature al ow-lying orbital for substrate activation. [1] Over the last decade there has been increasing interest in studying pnictogens,o ften considered Lewis basic given the availability of an energetically accessible lone pair, in this unconventional role.T his work has been expanded to include compounds of phosphorus, [2][3][4][5][6][7][8][9][10][11] arsenic, [12] antimony, [13][14][15][16][17][18][19][20] and bismuth. [21][22][23] By contrast, the reactivity of nitrogen-containing compounds as Lewis acids has been investigated to am uch lesser extent, largely due to the dearth of such species.C hloramines,n itrenes,d iazocarboxylates,azides,and diazonium salts have been shown to possess N-centered electrophilic behavior.…”

Section: Nitrenium Salts In Lewis Acid Catalysismentioning

confidence: 99%

Nitrenium Salts in Lewis Acid Catalysis

Mehta

Goicoechea

2020

Angew Chem Int Ed

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Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry.B yc ontrast, electrophilic nitrogencontaining compounds are muchr arer.N itrenium cations are an ew family of nitrogen-based Lewis acids,t he reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations.These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover,these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture,a llowing for benchtop transformations without the need to pretreat solvents.

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“…Over the last decade there has been increasing interest in studying pnictogens, often considered Lewis basic given the availability of an energetically accessible lone pair, in this unconventional role. This work has been expanded to include compounds of phosphorus, arsenic, antimony, and bismuth . By contrast, the reactivity of nitrogen‐containing compounds as Lewis acids has been investigated to a much lesser extent, largely due to the dearth of such species.…”

Section: Figurementioning

confidence: 99%

Nitrenium Salts in Lewis Acid Catalysis

Mehta

Goicoechea

2020

Angewandte Chemie

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Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents.

show abstract

Air- and water-stable Lewis acids: synthesis and reactivity of P-trifluoromethyl electrophilic phosphonium cations

Cited by 39 publications

References 49 publications

Lewis Superacids: Classifications, Candidates, and Applications

Lewis Superacids: Classifications, Candidates, and Applications

Nitrenium Salts in Lewis Acid Catalysis

Nitrenium Salts in Lewis Acid Catalysis

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