Palladium-Catalyzed Cross-Coupling Reactions of Silanolates: A Paradigm Shift in Silicon-Based Cross-Coupling Reactions

✍ Scribed by Scott. E. Denmark; John D. Baird

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 513 KB
• Volume: 12
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200600034

✦ Synopsis

Abstract

This paper chronicles the conceptual development, proof of principle experiments, and recent advances in the palladium‐catalyzed cross‐coupling reactions of the conjugate bases of organosilanols. The discovery that led to the design and refinement of this process represents a classical illustration of how mechanistic studies can provide a fertile ground for the invention of new reactions. On the basis of a working hypothesis (which ultimately proved to be incorrect) and the desire to effect silicon‐based cross‐coupling without the agency of fluoride activation, a mild and practical palladium‐catalyzed cross‐coupling of alkenyl‐, aryl‐, and heteroaryl silanolates has been developed. The mechanistic underpinnings, methodological extensions, and the successful applications of this technology to the synthesis of complex molecules are described.