Time‐Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions

Phillips, David Lee

doi:10.1002/9781118560907.ch7

Cited by 2 publications

(2 citation statements)

References 85 publications

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“…Several previous studies have demonstrated that photolysis of N-aminopyridinium salts provides nitrenium ions cleanly via heterolysis of the N-N bond. [42][43][44] Thus, stable products detected from this procedure can confidently be attributed to reactions of free nitrenium ions. Scheme 2 describes preparation of the corresponding N-aminopyridinium ion precursors (37 and 41) to cyclopropyl nitrenium ions (6 and 5, respectively).…”

Section: Generation Of Cyclopropylnitrenium Ions and Characterization...mentioning

confidence: 75%

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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Section: Generation Of Cyclopropylnitrenium Ions and Characterization...mentioning

confidence: 75%

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

Hong,

Falvey

2024

Preprint

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show abstract

“…Therefore, a photochemical route was chosen for the present study. Several previous studies have demonstrated that photolysis of N -aminopyridinium salts provides nitrenium ions cleanly via heterolysis of the N–N bond. − Thus, stable products detected from this procedure can confidently be attributed to reactions of free nitrenium ions.…”

Section: Results and Discussionmentioning

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.

show abstract

Time‐Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions

Cited by 2 publications

References 85 publications

Addition, Elimination, and Rearrangement 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

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

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