Palladium-Catalyzed Cross-Coupling Reactions of Silanolates.pdf

4954 2006 Wiley-VCH Verlag GmbH Co. KGaA, Weinheim Chem. Eur. J. 2006, 12, 4954 – 496 CONCEPTS DOI: 10.1002/chem.200600034 Palladium-Catalyzed Cross-Coupling Reactions of Silanolates: A Paradigm Shift i nSilicon-Based Cross-Coupling Reactions Scott. E. Denmark* and Joh nD. Baird[a] and versatile reaction.[6] The cross-coupling of organosilicon Abstract: This paper chronicles the conceptual develop- reagents features many advantages including the ease of ment, proof of principle experiments, and recent advan- preparation and purification of silanes, their low-molecular ces in the palladium-catalyzed cross-coupling reactions weight, and high stability. Moreover, the process generates of the conjugate bases of organosilanols. The discovery environmentally benign byproducts. that led to the design and refinement of this process Unlike the Stille and Negishi reactions, which require no represents a classical illustration of how mechanistic activation, or the Suzuki reaction, which requires only heat- studies can provide a fertile ground for the invention of ing with mild bases, silicon-based cross-coupling reactions new reactions. On the basis of a working hypothesis often require heating in the presence a fluoride source. Be- (which ultim