Sequential Processes in Palladium‐Catalyzed Silicon‐Based Cross‐Coupling

Although developed somewhat later, silicon‐based cross‐coupling has become a viable alternative to the more conventional Suzuki–Miyaura, Stille–Kosugi–Migita, and Negishi cross‐coupling reactions because of its broad substrate scope, high stability of silicon‐containing reagents, and low toxicity of waste streams. An empowering and yet underappreciated feature unique to silicon‐based cross‐coupling is the wide range of sequential processes available. In these processes, simple precursors are first converted to complex silicon‐containing cross‐coupling substrates, and the subsequent silicon‐based cross‐coupling reaction affords an even more highly functionalized product in a stereoselective fashion. In so doing, structurally simple and inexpensive starting materials are quickly transformed into value‐added and densely substituted products. Therefore, sequential processes are often useful in constructing the carbon backbones of natural products. In this review, studies of sequential processes involving silicon‐based cross‐coupling are discussed. Additionally, the total syntheses that utilize these sequential processes are also presented.