Lithium diisopropylamide-mediated ortholithiation of 2-fluoropyridines: rates, mechanisms, and the role of autocatalysis.

Lithium diisopropylamide (LDA)-mediated ortholithiations of 2-fluoropyridine and 2,6-difluoropyridine in tetrahydrofuran at -78 °C were studied using a combination of IR and NMR spectroscopic and computational methods. Rate studies show that a substrate-assisted deaggregation of LDA dimer occurs parallel to an unprecedented tetramer-based pathway. Standard and competitive isotope effects confirm post-rate-limiting proton transfer.

Mechanism of lithium diisopropylamide-mediated substitution of 2,6-difluoropyridine.

Treatment of 2,6-difluoropyridine with lithium diisopropylamide in THF solution at -78 degrees C effects ortholithiation quantitatively. Warming the solution to 0 degrees C converts the aryllithium to 2-fluoro-6-(diisopropylamino)pyridine. Rate studies reveal evidence of a reversal of the ortholithiation and a subsequent 1,2-addition via two monomer-based pathways of stoichiometries [ArH*i-Pr(2)NLi(THF)](double dagger) and [ArH*i-Pr(2)NLi(THF)(3)](double dagger).

Simple (imidazol-2-ylidene)-Pd-acetate complexes as effective precatalysts for sterically hindered Suzuki-Miyaura couplings.

[reaction: see text] A simplified synthesis of N-heterocyclic carbene (NHC)Pd-carboxylate complexes and their activity in Suzuki-Miyaura cross-coupling reactions are described. Coupling of sterically hindered aryl and activated alkyl chlorides bearing beta-hydrogens has been successfully achieved.

An industrially viable catalyst system for palladium-catalyzed telomerizations of 1,3-butadiene with alcohols.

The telomerization reaction of 1,3-butadiene with alcohols to give alkyl octadienyl ethers in the presence of palladium-carbene catalysts has been studied in detail. Unprecedented catalyst efficiency with turnover numbers (TON) up to 1,500,000 and turnover frequencies (TOF) up to 100,000 h(-1) have been obtained after optimization for the reaction of methanol in the presence of an excess of in situ generated carbene ligands. High yields (75-97 %) and catalyst productivities (TON 15,000-100,000) are observed for other aliphatic alcohols and phenols.

Synthesis, characterization, and catalytic activity of N-heterocyclic carbene (NHC) palladacycle complexes.

Palladacycle dimers possessing bridging halides can be easily cleaved by using N-heterocyclic carbenes (NHCs) to generate novel monomeric complexes. The structure of one of these was determined by single-crystal diffraction study and consists of a square-planar coordination around the palladium center where the NHC ligand is trans to the amine of the palladacycle. The complex was found to be equally active in aryl amination and alpha-arylation of ketones even at very low catalyst loading (0.

Well-defined, air-stable (NHC)Pd(Allyl)Cl (NHC = N-heterocyclic carbene) catalysts for the arylation of ketones.

A number of palladium-N-heterocyclic carbene (NHC) complexes were found to be active catalysts for the arylation of ketones. A large number of substrates, both aryl halides and ketones, are compatible with the reaction conditions. The ketone arylation reactions are achieved with low catalyst loading in short reaction times using aryl chlorides and triflates as reactive partners.

An air-stable palladium/N-heterocyclic carbene complex and its reactivity in aryl amination.

[reaction: see text] The synthesis and characterization of [Pd(IPr)Cl(2)](2) (1), an air- and moisture-stable complex, is reported. The utilization of 1 as a catalyst for amination of aryl chlorides and bromides with a variety of amine coupling partners under mild conditions is described. The amination reactions with 1 show a remarkable insensitivity to oxygen and water, and thus the amination reactions could be performed in air on the benchtop with undried reagent grade solvents and substrates with small effects on reaction times and conversions.