RESUMEN
The radical-mediated difunctionalization of 1,3-enynes facilitates rapid access to structurally diverse allenes and dienes. Whereas, owing to the existence of multiple active sites in conjugated 1,3-enynes, regulating selectivity in difunctionalized addition via a single transition-metal-catalyzed radical tandem process remains elusive. Herein, we disclose an intriguing protocol of substrate-controlled nickel-catalyzed regiodivergent sulfonylarylation of 1,3-enynes with the assistance of sulfonyl chlorides and arylboronic acids. This valuable synthetic utility respectively delivers a series of highly functionalized and synthetically challenging allenyl sulfones and dienyl sulfones from fine-tuned 1,3-enynes by one step, which provides a facile approach for complex sulfone-containing drug molecules synthesis.
RESUMEN
Functional group metathesis has the potential to render mild reaction conditions for C-H functionalization. Protocols for the meta- and ortho-C-H iodination of aniline derivatives via formal C(sp2)-H/C(sp2)-I metathesis using 2-nitrophenyl iodides as mild iodinating reagents are reported herein. These protocols led to the production of a range of valuable iodinated aniline derivatives. These results demonstrate the potential of developing novel site-selective C-H activation reactions with electron-rich compounds, since mild reagents can often been utilized in functional group metathesis reactions.