The invention of radical reactions. 30. Diazirines as carbon radical traps. Mechanistic aspects and synthetic applications of a novel and efficient amination process

doi:10.1021/JA00071A017

Paper

The invention of radical reactions. 30. Diazirines as carbon radical traps. Mechanistic aspects and synthetic applications of a novel and efficient amination process

Published Sep 1, 1993 · D. Barton, J. Jászberényi, E. Theodorakis

Journal of the American Chemical Society

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38

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0

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Abstract

A number of diazirines were synthesized for the purpose of exploring the addition of a carbon radical to the nitrogen-nitrogen double bond. Carbon radicals, generated from the photolysis of the 0-acyl derivatives of N-hydroxy- 2-thiopyridone or via radical exchange from the corresponding organotellurides, were shown to add smoothly to the diazirines leading to imines 34. When 3-(trifluoromethyl)-3-phenyldiazirine (13) is used as the trap, the thus formed imines can be easily hydrolyzed to amines. A mechanism that involves dimerization of the diaziridinyl radicals 32 to produce tetraazo intermediates 33 is suggested in accord with variable temperature NMR data for the reaction. Proof for this mechanistic scheme was furthermore obtained by isolation and X-ray structure determination of 33d. The first X-ray structure of a 3-(trifluoromethyl)-3-aryldiazirine is also reported.

Study Snapshot

Diazirines serve as efficient carbon radical traps, leading to imines that can easily be hydrolyzed to amines, with a mechanism involving dimerization of diaziridinyl radicals.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

The invention of radical reactions. 30. Diazirines as carbon radical traps. Mechanistic aspects and synthetic applications of a novel and efficient amination process

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References

Citations

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Photocatalytic reactions enable the synthesis of intricate and functionalized compounds, offering a promising future for the chemical synthesis of pharmaceuticals.

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The electrophilic potential of diazirines can efficiently synthesize indomethacin, an anti-inflammatory drug, in a single step.

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Radical decarboxylative carbon-nitrogen bond formation from carboxylic acids and their derivatives is a valuable tool in modern synthetic chemistry for synthesis of complex natural products.

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Peptide scaffolds with a C-terminal Gly yield 21-26% of cross-linked products in gas-phase cations, with a significant fraction of cross-links involving Gly amide and carboxyl groups.

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This study presents a mild, robust, and selective method for efficiently constructing functionalized diazirines from carbohydrazide and diazo-substituted hypervalent iodine reagents, successfully converting various aryl, alkyl, benzyl, and hetero

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Diazirine methacrylamide (DZMA) improves in-gel protein capture for immunoassays, reducing background fluorescence and non-specific interactions, but has lower capture efficiency in open microfluidic systems.

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This research demonstrates a facile, metal-free method for synthesis of nitrogen-containing molecules with diverse structural diversity, benefiting chemical biology and drug discovery.

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Dialkyldiazirine photoaffinity probes are unique tools for studying small molecule-protein interactions, revealing hidden cholesterol binding sites in Hedgehog morphogen proteins.