Nickel‐Catalyzed Reductive Coupling of Aryl Tosylates With Chlorosilanes: A General Approach to Arylvinylsilanes

The development of efficient catalytic systems for constructing C─Si bonds from stable and readily available electrophiles represents an important objective in synthetic chemistry. Herein, we describe a practical nickel‐catalyzed reductive cross‐coupling reaction for the direct silylation of aryl tosylates with chlorosilanes. This method employs a well‐defined catalytic system comprising Ni(Py) 4 Cl 2 and 4,4'‐di‐tert‐butyl‐2,2'‐bipyridine with manganese powder as the reductant. It affords a diverse range of arylsilanes in moderate to excellent yields under mild conditions. The reaction demonstrates a broad substrate scope and exceptional functional group tolerance, accommodating variously substituted aryl tosylates, including fused aromatic and heteroaromatic systems. The obtained arylvinylsilanes serve as versatile building blocks for further derivatization. The synthetic utility of the methodology is highlighted by its successful gram‐scale operation, underscoring its potential for practical synthesis.