Hiyama Cross-Coupling Research Articles

A New Stereoselective Approach to (E)-Poly(arylenevinylene)s

A new synthetic protocol for the one-pot, stereoselective synthesis of ( E)-poly(arylenevinylene)s via palladium-catalyzed Hiyama cross-coupling of dihaloarenes with cyclic GEM-bis(silyl)ethene or isopropoxydimethylvinylsilane is described.

Formal synthesis of tubelactomicins via a transannular Diels–Alder approach

A formal synthesis of the antimicrobial tricyclic macrolides, tubelactomicins A and E, featured by a transannular Diels–Alder (TADA) approach, has been explored. The key issue for the transannular cyclization was the synthesis of a 24-membered macrolactone equipped with all the requisite functionalities, which has been achieved using an intramolecular Hiyama cross-coupling strategy. The Hiyama coupling reaction spontaneously triggered off the TADA reaction. From the endo-TADA adduct, formal syntheses of tubelactomicins A and E were achieved. The 24-membered macrolactone formation was also achieved via an intramolecular ring-closing metathesis approach.

Improved Procedure for Palladium‐Catalyzed Hiyama Cross‐Coupling Reaction of Aryl Halides with Aryltrimethoxysilanes under Solvent‐Free Conditions.

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Palladium-coated nickel nanoclusters: new Hiyama cross-coupling catalysts

The advantages of bimetallic nanoparticles as C-C coupling catalysts are discussed, and a simple, bottom-up synthesis method of core-shell Ni-Pd clusters is presented. This method combines electrochemical and 'wet chemical' techniques, and enables the preparation of highly monodispersed structured bimetallic nanoclusters. The double-anode electrochemical cell is described in detail. The core-shell Ni-Pd clusters were then applied as catalysts in the Hiyama cross-coupling reaction between phenyltrimethoxysilane and various haloaryls. Good product yields were obtained with a variety of iodo- and bromoaryls. We found that, for a fixed amount of Pd atoms, the core-shell clusters outperform both the monometallic Pd clusters and the alloy bimetallic Ni-Pd ones. THF is an excellent solvent for this process, with less than 2% homocoupling by-product. The roles of the stabiliser and the solvent are discussed.

Improved Procedure for Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl Halides with Aryltrimethoxysilanes under Solvent-Free Conditions

An improved palladium-catalyzed Hiyama cross-coupling reaction is reported. In the presence of PdCl 2 (MeCN) 2 , P(o-tol) 3 and TBAF, a number of ArX (X = I, Br, Cl) were coupled with ArSi(OMe) 3 efficiently to afford the desired cross-coupled products in moderate to excellent yields. It is noteworthy that this protocol is conducted under relatively low Pd loadings and solvent-free conditions.

Isolation of the Transmetalation Step in the Hiyama Cross-Coupling Reaction of Organosilanes

The oxidative addition of o-(Me2RSiCH2O)C6H4I (R = Me, Ph, F) to palladium(0) complexes leads to the corresponding complexes o-(Me2RCH2O)C6H4Pd(L2)I (L = PPh3, AsPh3; L2 = dppf). The intramolecular Pd/Si transmetalation proceeds smoothly with fluorides and carbonates as the promoters.