Unusual reactivity of N-tert-butylimines under FVT conditions

Leśniak, Stanisław; Pasternak, Beata; Justyna, Katarzyna; Vu, Thien Y.; Huỳnh, Thị Kiều Xuân; Khayar, Saïd; Dargelos, Alain; Chrostowska, Anna

doi:10.1016/j.tet.2012.10.090

Cited by 9 publications

(3 citation statements)

References 41 publications

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“…Thirdly, the major cyclic product is 1,2‐dimethylindole ( 6 ), a compound that cannot be formed by any of the pathways previously described for imines 6. 7…”

Section: Resultsmentioning

confidence: 99%

“…described transformations of iminyl radicals into aza‐heterocycles under the conditions of FVT. In our recent work,7 we have demonstrated that elimination of isobutene from aliphatic N ‐ tert ‐butylimines 1 may take place (Scheme ), but in some cases the course of the reaction is entirely different, leading instead to the formation of N ‐ heterocycles 2 or 4 .…”

Section: Introductionmentioning

confidence: 99%

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New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

Chrostowska

Huỳnh

et al. 2013

Chemistry A European J

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Thermal reactions of N-benzylidene- and N-(2-pyridylmethylidene)-tert-butylamines (5 and 13) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2-dimethylindole and 3-methylisoquinoline. In the reaction of 13 at 800 °C, 3-methylimidazo[1,5-a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV-photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ.

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“…Thirdly, the major cyclic product is 1,2‐dimethylindole ( 6 ), a compound that cannot be formed by any of the pathways previously described for imines 6. 7…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

Chrostowska

Huỳnh

et al. 2013

Chemistry A European J

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“…However, a short while ago, we reported unusual reactions of N ‐ tert ‐butylimines under FVT conditions, namely, the elimination of a methyl radical and subsequent formation of N ‐heterocycles 2. Thus, FVT of N‐tert ‐butyl‐ E ‐crotonaldimine at 800 °C leads to the formation of pyrrole and crotonitrile, whereas 1,4‐di( tert ‐butyl)‐1,4‐diazabuta‐1,3‐diene affords 2‐methylimidazole 2a…”

Section: Introductionmentioning

confidence: 99%

Flash Vacuum Thermolysis of N‐(3‐ and 4‐Pyridylmethylidene)‐tert‐butylamines: Mechanisms of Formation of Pyrrolopyridines and Naphthyridines

Justyna¹,

Leśniak²,

Nazarski³

et al. 2014

Eur J Org Chem

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Pyrrolopyridines and naphthyridines are formed by flash vacuum thermolysis (FVT) of 3‐ and 4‐pyridylmethylidene‐tert‐butylimines 8 and 15. Elimination of a methyl radical generates resonance stablized 2‐azaallyl radicals a1 and b1. The formation of pyrrolopyridines 9, 16 and 17 is rationalized in terms of cyclization of 1‐aziridinyl radicals a2 and b2. Formation of naphthyridine 10 from imine 8, and of 11 and 18 from imine 15, are in accord with cyclization of 1‐azaallyl radicals a6 and b9. Formation of naphthyridine 11 from 8, and of 10 and 19 from 15, indicate the operation of the spiro‐cyclization pathways forming intermediates a9 and b14. Formation of the 1,8‐naphthyridine 20 (3 %) indicates a rearrangement through aziridine b22 and biradical b23. DFT calculations at the CAM‐B3LYP/6‐311G(d,p) level support the proposed reaction mechanisms.

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Direkte Synthese von funktionalisierten 1,2‐Azaborininen

et al. 2014

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Ein neuer katalytischer Zugang zu funktionalisierten 1,2-Azaborininen konnte durch [2+2]/[2+4]-Cycloadditionen von Di-tert-butyliminoboranen und Alkinen in Gegenwart eines Rhodiumkatalysators erçffnet werden. Die ersten Beispiele für Ferrocen-funktionalisierte Azaborinine konnten so synthetisiert werden. Außerdem kann die Regioselektivität dieser Reaktion über die Bildung eines intermediären Rhodium-1,2-Azaboret-Komplexes kontrolliert werden, was zu einem ersten Azaborininboronsäureester führte. Die Isolierung eines BN-Isosters mit einer NH-Gruppe wurde durch Eliminierung von Isobuten aus einer N(tBu)-Einheit unter thermolytischen Bedingungen erreicht. Quantenchemische Untersuchungen liefern weitere Einblicke in die Bildung von 1,2-Azaborininen und die Eliminierung von Isobuten aus der N(tBu)-Gruppe.

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Unusual reactivity of N-tert-butylimines under FVT conditions

Cited by 9 publications

References 41 publications

New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

Flash Vacuum Thermolysis of N‐(3‐ and 4‐Pyridylmethylidene)‐tert‐butylamines: Mechanisms of Formation of Pyrrolopyridines and Naphthyridines

Direkte Synthese von funktionalisierten 1,2‐Azaborininen

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