C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine

Guo, Ting; Li, Jinghao; Cui, Zhangkai; Wang, Zefan; Lu, Hongjian

doi:10.1038/s44160-024-00559-9

Nat. Synth

2024

DOI: 10.1038/s44160-024-00559-9

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C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine

Ting Guo,

Jinghao Li,

Zhangkai Cui

et al.

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2024

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Cited by 4 publications

References 54 publications

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Synthesis of Substituted Tetralins via Nitrogen Deletion/Diels–Alder Cascade Reaction

Zang,

Ye,

Cheng

et al. 2024

J. Org. Chem.

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Skeletal editing is an important approach for the modification and diversification of biologically active molecules. The utilization of nitrogen deletion strategies in skeletal editing has recently emerged as a new method for compound modification. Here, we report an unexpected nitrogen deletion in isoindolines. Contrary to the anticipated outcome of cyclobutane formation via intramolecular radical couplings, the nitrogen deletion of isoindoline triggers a Diels−Alder cycloaddition facilitated by the in situ formation of ortho-xylylene to yield tetraline. Inspired by this reaction, we developed a new strategy for synthesizing substituted tetralins, employing isoindoline, nitrogen deletion reagent (anomeric amide), and dienophiles. This methodology demonstrates a new pathway for tetralin synthesis and the modification and diversification of isoindolines.

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Synthesis of Substituted Tetralins via Nitrogen Deletion/Diels–Alder Cascade Reaction

Zang,

Ye,

Cheng

et al. 2024

J. Org. Chem.

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Photoredox/Iron Dual-Catalysis-Enabled [4 + 2] Cyclization of Acyl Nitrene with Alkynes

Xie,

Tang,

Hou

et al. 2024

Org. Lett.

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In this work, the annulation of acyl nitrene with alkynes is reported under photoredox/iron dual-catalysis for the synthesis of a series of isoquninalin-2-ones. The reaction is featured with a high reaction regioselectivity and good reaction generality. In particular, the resulting isoquinalin-2-ones could be structurally elaborated into several biologically interesting scaffolds. Mechanism investigation suggests that the reaction was ascribed to a formal [4 + 2] cyclization. It is believed that this reaction represents an initial example of preparing isoquinolin-1-ones from ferric peroxylcatalyzed nitrene insertion.

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Skeletal Editing of Mechanically Interlocked Molecules: Nitrogen Atom Deletion from Crown Ether-Dibenzylammonium Rotaxanes

Gauthier,

Whittingham,

Hasija

et al. 2024

J. Am. Chem. Soc.

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Removing the nitrogen atom from secondary amines while simultaneously linking the remaining fragments is a powerful form of late-stage skeletal editing. Here, we report its use for the deletion of the nitrogen atom of the dibenzylammonium template used to assemble crown ether rotaxanes. The reaction uses an anomeric amide that activates secondary amines to generate a carbon−carbon bond that replaces the amine nitrogen. Despite the potential for dethreading of the intermediate diradical pair, the nitrogen atom was successfully deleted from a series of rotaxane axles as long as the macrocycle could access coconformations that did not inhibit the reaction of the amine group. The skeletally edited interlocked molecules were obtained directly from the parent crown ether-dibenzylammonium rotaxanes in modest yields (23−36%) and characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. One skeletally edited rotaxane shows a network of weak CH•••O hydrogen bonds between the crown ether and benzylic methylene groups of the axle in the solid state, in place of the crown etherammonium binding motif used to assemble the parent, unedited, rotaxane.

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C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine

Cited by 4 publications

References 54 publications

Synthesis of Substituted Tetralins via Nitrogen Deletion/Diels–Alder Cascade Reaction

Synthesis of Substituted Tetralins via Nitrogen Deletion/Diels–Alder Cascade Reaction

Photoredox/Iron Dual-Catalysis-Enabled [4 + 2] Cyclization of Acyl Nitrene with Alkynes

Skeletal Editing of Mechanically Interlocked Molecules: Nitrogen Atom Deletion from Crown Ether-Dibenzylammonium Rotaxanes

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