The combination of 20 mol % of copper iodide and lithium tert-butoxide triggers the formation of a broad range of substituted, functionalized α-alkoxy 2H-naphthalenones from readily available N-tosylhydrazones. The data suggests that this transformation occurs through cycloaddition of a copper carbenoid with an ester, followed by a Lewis acid-catalyzed [1,2] alkyl shift of the in situ generated alkoxyepoxide intermediate.

The combination of 20 mol % of copper iodide and lithium tert-butoxide triggers the formation of a broad range of substituted, functionalized α-alkoxy 2H-naphthalenones from readily available N-tosylhydrazones. The data suggests that this transformation occurs through cycloaddition of a copper carbenoid with an ester, followed by a Lewis acid-catalyzed [1,2] alkyl shift of the in situ generated alkoxyepoxide intermediate.

Dirhodium(II)-carboxylate complexes were discovered to promote the selective migration of acyl groups in trisubstituted styryl azides to form 1,2,3-trisubstituted indoles. The styryl azides are readily available in three steps from cyclobutanone and 2-iodoaniline.

A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition-metal-catalyzed CH-bond functionalization. In addition to modifying the substituents present on the end-pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution-state properties and field-effect-transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λ_max value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin-film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm² V⁻¹ s⁻¹ and the I_on/I_off value is greater than 10⁶.

Dirhodium(II)-carboxylate complexes were discovered to promote the selective migration of acyl groups in trisubstituted styryl azides to form 1,2,3-trisubstituted indoles. The styryl azides are readily available in three steps from cyclobutanone and 2-iodoaniline.

The construction of N-heterocycles remains a fertile area of research because of their ubiquitous occurrence in biologically active small molecules and materials. Their ubiquitous nature has motivated the development of methods to streamline their synthesis. Formation of the C–N bond via transition metal-functionalization of the aryl or vinyl C–H bond simplifies N-heterocycle synthesis by minimizing the manipulation of functional groups. Transition metal-catalyzed C–H bond amination can be accomplished through two strategies: the activation of the N-atom or activation of the C–H bond. This microreview examines the recent advances in applying these two strategies for the functionalization of sp² C–H bonds and is organized by the source of nitrogen atom.