Palladium-Catalyzed Cross-Coupling Reactions of Organosilanols and Their Salts.pdf

Palladium-Catalyzed Cross-Coupling Reactions of Organosilanols and Their Salts: Practical Alternatives to Boron- and Tin-Based Methods SCOTT E. DENMARK* AND CHRISTOPHER S. REGENS Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801 RECEIVED ON FEBRUARY 2, 2008 C O N S P E C T U S n the panoply of modern synthetic methods for forming carbon-carbon and carbon-heteroatom bonds, the transition Imetal-catalyzed cross-coupling of organometallic nucleophiles with organic electrophiles enjoys a preeminent status. The preparative utility of these reactions is, in large measure, a consequence of the wide variety of organometallic donors that have been conscripted into service. The most common of these reagents are organic derivatives of tin, boron, and zinc, which each possess unique advantages and shortcomings. Because of their low cost, low toxicity, and high chemical stability, orga- nosilanes have emerged as viable alternatives to the conventional reagents in recent years. However, unlike the tin- and zinc-based reactions, which require no activation, or the boron-based reactions, which require only heating with mild bases, silicon-based cross-coupling reactions often require heating in the presence of a fluoride source; this has significantly ham- pered the widespread acceptance of organosilanes. To address the “fluoride problem”, we have introduced a new paradigm for palladium-catalyzed, silicon-based cross- coupling reactions that employs organosilan