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A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C-H bonds.

ABSTRACT: A highly tunable radical-mediated reaction system for the functionalization of tertiary aliphatic C-H bonds was developed. Reactions of various substrates with the Zhdankin azidoiodane reagent 1, Ru(bpy)₃Cl₂, and visible light irradiation at room temperature gave C-H azidated or halogenated products in an easily controllable fashion. These reactions are efficient, selective, and compatible with complex substrates. They provide a potentially valuable tool for selectively labeling tertiary C-H bonds of organic and biomolecules with tags of varied chemical and biophysical properties for comparative functional studies.

SUBMITTER: Wang Y

PROVIDER: S-EPMC5477033 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C-H bonds.

Wang Yaxin Y Li Guo-Xing GX Yang Guohui G He Gang G Chen Gong G

Chemical science 20160111 4

A highly tunable radical-mediated reaction system for the functionalization of tertiary aliphatic C-H bonds was developed. Reactions of various substrates with the Zhdankin azidoiodane reagent 1, Ru(bpy)3Cl2, and visible light irradiation at room temperature gave C-H azidated or halogenated products in an easily controllable fashion. These reactions are efficient, selective, and compatible with complex substrates. They provide a potentially valuable tool for selectiv ...[more]

PMID: 28660040

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Project description:Many enzymes oxidize unactivated aliphatic C-H bonds selectively to form alcohols; however, biological systems do not possess enzymes that catalyse the analogous aminations of C-H bonds. The absence of such enzymes limits the discovery of potential medicinal candidates because nitrogen-containing groups are crucial to the biological activity of therapeutic agents and clinically useful natural products. In one prominent example illustrating the importance of incorporating nitrogen-based functionality, the conversion of the ketone of erythromycin to the -N(Me)CH2- group in azithromycin leads to a compound that can be dosed once daily with a shorter treatment time. For such reasons, synthetic chemists have sought catalysts that directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited to the intermolecular functionalization of complex molecules because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom. Among C-H bond amination reactions, those forming a C-N bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to form from ketones or alcohols that might be created in a biosynthetic pathway by oxidation. Here we report a mild, selective, iron-catalysed azidation of tertiary C-H bonds that occurs without excess of the valuable substrate. The reaction tolerates aqueous environments and is suitable for the functionalization of complex structures in the late stages of a multistep synthesis. Moreover, this azidation makes it possible to install a range of nitrogen-based functional groups, including those from Huisgen 'click' cycloadditions and the Staudinger ligation. We anticipate that these reactions will create opportunities to modify natural products, their precursors and their derivatives to produce analogues that contain different polarity and charge as a result of nitrogen-containing groups. It could also be used to help identify targets of biologically active molecules by creating a point of attachment--for example, to fluorescent tags or 'handles' for affinity chromatography--directly on complex molecular structures.

Dataset Information

A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C-H bonds.

Publications

A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C-H bonds.

Similar Datasets

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