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2.1.6.2.5 Azides as the Nitrogen-Atom Source

DOI: 10.1055/sos-SD-208-00180

Driver, T. G.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20132322.

More recent progress has also been achieved using azides as the metal nitrene precursor. Aryl azides 51 are used in the amination of secondary benzylic C—H bonds to afford 2-aryl-substituted indolines 52 and indoles 53 using 2 mol% of an iridium(I) catalyst at room temperature (Scheme 11).[‌61‌] The electronic constraints of this reaction are similar to the examples described above: high conversions are possible only when the starting aryl azide is substituted with a strongly electron-withdrawing group. In contrast, no such electronic constraints are observed at the benzylic site: both electron-rich and electron-deficient arenes are tolerated. In every case, the indoline product is unstable toward silica gel and purification using flash column chromatography affords a separable mixture of indoline and indole.

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References