The Pyridyldiisopropylsilyl Group: A Masked Functionality and Directing Group for Monoselective ortho-Acyloxylation and ortho-Halogenation Reactions of Arenes was written by Huang, Chunhui;Chernyak, Natalia;Dudnik, Alexander S.;Gevorgyan, Vladimir. And the article was included in Advanced Synthesis & Catalysis in 2011.Computed Properties of C10H10BrN This article mentions the following:
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 via two complementary routes using easily available 2-(diisopropylsilyl)pyridine (I). The first strategy features a nucleophilic hydride substitution at the silicon atom in I with aryllithium reagents generated in situ from the corresponding aryl bromides or iodides. The second milder route exploits a highly efficient room-temperature rhodium(I)-catalyzed cross-coupling reaction between I 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-ortho-acyloxylation and ortho-halogenation of various aromatic compounds Most importantly, 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 via the Hiyama-Denmark cross-coupling reaction is feasible for the acetoxylated products. Moreover, the ortho-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 intramol. primary kinetic isotope effect (kH/kD = 6.7). Based on these observations, a general mechanism involving the formation of a palladacycle via a C-H activation process as the rate-determining step has been proposed. In the experiment, the researchers used many compounds, for example, 5-Bromo-2,3-dimethyl-1H-indole (cas: 4583-55-5Computed Properties of C10H10BrN).
5-Bromo-2,3-dimethyl-1H-indole (cas: 4583-55-5) belongs to indole derivatives. Indole, first isolated in 1866, and it is commonly synthesized from phenylhydrazine and pyruvic acid, although several other procedures have been discovered. In addition to indole, the strain-release chemistry worked for numerous substrates including amines, alcohols, thiols, carboxylic acids, imidazoles, and pyrazoles.Computed Properties of C10H10BrN
Referemce:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles