Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols With Aryl and Heteroaryl Iodides via Thiyl Radicals

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• 作者：Martins S. Oderinde ; Mathieu Frenette ; Daniel W. Robbins ; Brian Aquila ; Jeffrey W. Johannes
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 17, 2016
• 年：2016
• 卷：138
• 期：6
• 页码：1760-1763
• 全文大小：396K
• ISSN：1520-5126

文摘

Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C–S cross-coupling was achieved versus competitive C–O and C–N cross-couplings. This C–S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C–S cross-coupling reaction does not involve a Ni(0)-species.