Electrophilic Aminating Agents in Total Synthesis

O'Neil, Lauren G.; Bower, John F.

doi:10.1002/ange.202102864

Cited by 7 publications

(3 citation statements)

References 379 publications

(645 reference statements)

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“…Nitrenium ions can be produced through several methods, including solvolysis of N -chloramines and oxidation of amines using hypervalent iodonium salts. − However, these routes can also produce stable products from concerted reactions in addition to those from true nitrenium intermediates. Therefore, a photochemical route was chosen for the present study.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The oil was purified via column chromatography (12% ethyl acetate in hexanes), which yielded nitrosamine 39 (8.37 g, 81.3%) as an inseparable mixture of two geometric isomers that matched the literature values. 1 1-Benzyl-1-cyclopropylhydrazine (40). The compound was synthesized using a modified literature procedure.…”

Section: -([11′-biphenyl]-4-yl)-1-cyclopropylhydrazine (36)mentioning

confidence: 99%

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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: Results and Discussionmentioning

confidence: 99%

Section: -([11′-biphenyl]-4-yl)-1-cyclopropylhydrazine (36)mentioning

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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“…Nitrenium ions can be produced through several methods, including solvolysis of N-chloramines 37 and oxidation of amines using hypervalent iodonium salts. [38][39][40][41] However, these routes can also produce stable products from concerted reactions in addition to those from true nitrenium intermediates. Therefore, a photochemical route was chosen for the present study.…”

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

confidence: 99%

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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Copper(I)‐Catalyzed Asymmetric Synthesis of P‐Chiral Aminophosphinites

Tian

Zhang

et al. 2022

Angewandte Chemie

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Herein, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines is developed. In the cases of symmetrical diarylphosphines, a series of aminophosphinites is prepared in high yields.In the cases of unsymmetrical diarylphosphines, an array of P-chiral aminophosphinites is synthesized in high yields with high enantioselectivity by using a copper(I)-(R,R P )-Ph-FOXAP complex as a chiral catalyst. Based on several control experiments and 31 P NMR studies, a two-electron redox mechanism involving the dynamic kinetic asymmetric transformation of unsymmetrical diarylphosphines is proposed for the copper(I)-catalyzed asymmetric reaction. Finally, one representative P-chiral phosphoric amide generated through the oxidation with H 2 O 2 is transformed to a chiral diarylphosphinate in high yield with retained enantioselectivity, which allows further transformations towards various P-chiral tertiary phosphines.

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Electrophilic Aminating Agents in Total Synthesis

Cited by 7 publications

References 379 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

Copper(I)‐Catalyzed Asymmetric Synthesis of P‐Chiral Aminophosphinites

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