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The C–S cross‐coupling reaction is a very efficient and powerful tool for constructing C–S bonds. Despite the well‐reported C–S cross‐coupling protocols using aryl halides, this reaction using sp2‐hybridized nonaromatic halides is still challenging. Herein, we report light‐assisted C–S cross‐coupling between thiols and 5‐chlorobenzofurazan under blue LED irradiation. We used a new nickel catalyst to synthesize 11 unpublished compounds. Furthermore, we assessed the mechanism and the influence of light irradiation on this reaction and proposed a plausible mechanism that is mediated by the excited state of the nickel catalyst promoted by irradiation with blue light and the C–S coupling product formed. Notably, C–S cross‐coupling under light irradiation was performed for the first time using a nickel catalyst in the absence of an external photocatalyst. We demonstrated that because nickel has a low energy barrier for oxidative addition, this protocol proceeded efficiently using chlorine as a leaving group, and the excited state of the nickel catalyst promoted reductive elimination with a lower energy barrier. It is important to mention that the procedure was tolerated by many functional groups within the thiol, affording a greater than 99% yield after reacting for 6 h. [ABSTRACT FROM AUTHOR]

The palladium-catalyzed Suzuki–Miyaura cross-coupling reaction is one of the most important and efficient reactions to prepare a variety of organic compounds, including biaryls. Despite the overwhelming number of reports related to this topic, some methodological difficulties persist in terms of catalyst handling, recovery, and reuse, as well as the reaction media. This work reports the rational design of new, efficient, cost-effective, and reusable palladium catalysts supported on synthetic talc for the Suzuki–Miyaura reaction. From the results, key points were identified: both designed catalysts accelerated the reaction in EtOH and an open-flask setup, affording moderate to excellent yields within a short time (e.g., 30 min) even for deactivated aryl halides; the protocol can be applied to a great number of both cross-coupling partners, showing an excellent functional group tolerance; the catalysts can be recovered and reused without significant loss of activity. This protocol was used for the synthesis of a precursor of angiotensin II inhibitors such as valsartan, losartan, irbesartan, and telmisartan. [ABSTRACT FROM AUTHOR]