The Pyridyldiisopropylsilyl Group: A Masked Functionality and Directing Group for Monoselective -Acyloxylation and -Halogenation Reactions of Arenes.

A novel, easily removable and modifiable silicon-tethered pyridyldiisopropylsilyl directing group for C-H functionalizations of arenes has been developed. The installation of the pyridyldiisopropylsilyl group can efficiently be achieved two complementary routes using easily available 2-(diisopropylsilyl)pyridine (). The first strategy features a nucleophilic hydride substitution at the silicon atom in with aryllithium reagents generated from the corresponding aryl bromides or iodides. The second milder route exploits a highly efficient room-temperature rhodium(I)-catalyzed cross-coupling reaction between and aryl iodides. The latter approach can be applied to the preparation of a wide range of pyridyldiisopropylsilyl-substituted arenes possessing a variety of functional groups, including those incompatible with organometallic reagents. The pyridyldiisopropylsilyl directing group allows for a highly efficient, regioselective palladium(II)-catalyzed mono--acyloxylation and -halogenation of various aromatic compounds. Most impor-tantly, the silicon-tethered directing group in both acyloxylated and halogenated products can easily be removed or efficiently converted into an array of other valuable functionalities. These transformations include protio-, deuterio-, halo-, boro-, and alkynyldesilylations, as well as a conversion of the directing group into the hydroxy functionality. In addition, the construction of aryl-aryl bonds the Hiyama-Denmark cross-coupling reaction is feasible for the acetoxylated products. Moreover, the -halogenated pyridyldiisopropylsilylarenes, bearing both nucleophilic pyridyldiisopropylsilyl and electrophilic aryl halide moieties, represent synthetically attractive 1,2-ambiphiles. A unique reactivity of these ambiphiles has been demonstrated in efficient syntheses of arylenediyne and benzosilole derivatives, as well as in a facile generation of benzyne. In addition, preliminary mechanistic studies of the acyloxylation and halogenation reactions have been performed. A trinuclear palladacycle intermediate has been isolated from a stoichiometric reaction between diisopropyl-(phenyl)pyrid-2-ylsilane () and palladium acetate. Furthermore, both C-H functionalization reactions exhibited equally high values of the intramolecular primary kinetic isotope effect (/ = 6.7). Based on these observations, a general mechanism involving the formation of a palladacycle a C-H activation process as the rate-determining step has been proposed.