Aryl Nitrenium Ions in Aqueous Solution

Novák, Michael; Wang, Yue‐Ting

doi:10.1002/9781118560907.ch4

Cited by 2 publications

(4 citation statements)

References 216 publications

(498 reference statements)

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“…Nitrenium ions are reactive intermediates characterized by a dicoordinate nitrogen atom bearing a formal positive charge (R-N-R′ + ). − These species can be derived from a net two-electron oxidation of amines or through a net 4-electron reduction of nitro compounds. The detailed understanding of nitrenium ion behavior is needed in order to identify or exclude the involvement of these species in chemical and biological processes that entail oxidation or reduction of nitrogen-containing compounds.…”

Section: Introductionmentioning

confidence: 99%

Rearrangement, Elimination, and Ring-Opening Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

Hong,

Falvey

2024

J. Org. Chem.

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N-(4-Biphenylyl)-N-cyclopropyl nitrenium ion 5 and N-benzyl-N-cyclopropyl nitrenium ion (6) were generated through photolysis of their corresponding N-aminopyridinium ion photoprecursors. In the case of 5, stable products result from a combination of cyclopropyl ring expansion (N-biphenylazetium ion) and ethylene elimination (biphenylisonitrilium ion). When present in high concentrations, methanol can add to the cyclopropyl ring-forming N-3-methoxypropyl-N-biphenyl iminium ion. In contrast, the only detectable product from the N-benzyl-N-cyclopropyl nitrenium ion ( 6) is benzylisonitrile, resulting from the elimination of ethylene. Density functional theory (DFT) calculations predict the product distributions from the more stable biphenyl system 5 with reasonable accuracy. However, product distributions from the less stable benzyl system 6 are forecast with less accuracy.

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Section: Introductionmentioning

confidence: 99%

Rearrangement, Elimination, and Ring-Opening Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

Hong,

Falvey

2024

J. Org. Chem.

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“…However product distributions from the less stable benzyl system 6 are forecast with less accuracy.Nitrenium ions are reactive intermediates characterized by a di-coordinate nitrogen atom bearing a formal positive charge. [1][2][3][4][5] These species can be derived from a net two-electron oxidation of amines or through a net 4-electron reduction of nitro compounds. Detailed understanding of nitrenium ion behavior is needed in order to identify, or exclude, the involvement of these species in chemical and biological processes that entail oxidation or reduction of nitrogen-containing compounds.In particular, the oxidation of cyclopropyl amines, 1 is involved in a surprising variety of important reactions, including synthetic transformations, 6-8 the treatment of depression through the inactivation of monoamine oxidases, 9-13 and has been used as a mechanistic probe.…”

mentioning

confidence: 99%

“…Nitrenium ions are reactive intermediates characterized by a di-coordinate nitrogen atom bearing a formal positive charge. [1][2][3][4][5] These species can be derived from a net two-electron oxidation of amines or through a net 4-electron reduction of nitro compounds. Detailed understanding of nitrenium ion behavior is needed in order to identify, or exclude, the involvement of these species in chemical and biological processes that entail oxidation or reduction of nitrogen-containing compounds.…”

mentioning

confidence: 99%

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Addition, Elimination, and Rearrangement Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

Hong,

Falvey

2024

Preprint

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Two cyclopropyl substituted nitrenium ions were generated through photolysis of their corresponding N-aminopyridinium ion photoprecursors. In the case of N-biphenyl-N-cyclopropyl nitrenium ion (5). Stable products are derived from a combination of cyclopropyl ring expansion, forming N-biphenylazetium ion, and ethylene elimination, forming biphenylisonitrilium ion. When present in high concentrations, methanol can add to the cyclopropyl ring forming N-3-methoxypropyl-N-biphenyl iminium ion. In contrast, the only detectable product from N-benzyl-N-cyclopropyl nitrenium ion (6) is benzylisonitrile, resulting from elimination of ethylene. DFT calculations predict the product distributions from the more stable biphenyl system 5 with reasonable accuracy. However product distributions from the less stable benzyl system 6 are forecast with less accuracy.

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Aryl Nitrenium Ions in Aqueous Solution

Cited by 2 publications

References 216 publications

Rearrangement, Elimination, and Ring-Opening Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

Rearrangement, Elimination, and Ring-Opening Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

Addition, Elimination, and Rearrangement Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation

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