tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergo electrocyclic ring closure to yield hydroxynaphthalenes a...

A conceptually new, simple and practical method for the syn-nucleophilic displacement of aryl and vinyl epoxides and aryl aziridines with (substituted) phenols, using aryl borates as activating nucleophiles under neutral conditions, is reported.

Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from com...

An orthogonal set of Cu-catalysts for the selective mono-arylation of alkyl aryl diols using aryl iodides is presented. Picolinic acid ligated copper catalyst provided phenol O-arylation only, while alkyl aryl ethers are generated by ligand-free copper catalyst in the presence of 2 equivalents NaOt-Bu.

A Pd-catalyzed addition of boronic acids to ynol ethers has been realized, delivering trisubstituted vinyl ethers in good yields with perfect control of the regio- and stereoselectivity. The reaction proceeds under mild conditions and exhibits excellent functional group compatibility. Moreover, the resultant products can be converted into pentasubstituted benzenes via the tandem Diels-Alder/aro...

Aryl ethers are important linking units in the structure of lignins and low rank coals that are thermally labile at 375°C. Mass transport limitations experienced in these cross-linked macromolecular solids can lead to alterations in thermochemical processing kinetics and product yields. The molecular level details of these alterations on reaction pathways are revealed through studies of model c...

The cycloaddition reaction of acylketenes with vinyl ethers affords an extremely direct route to 2,6-dideoxysugars and their methyl ethers. The lithium enolate of commercial 2,6,6-trimethyldioxinone 3 was fluorinated in good yield to afford fluorinated dioxinone 8. An illustrative range of fluorinated 2,6-dideoxysugar derivatives was prepared via the acetyl ketene-vinyl ether cycloadduct. Elect...

Palladium(II) complexes catalyze the formation of enamides via the formal cross-coupling reaction between nitrogen nucleophiles and vinyl ethers. These vinyl transfer reactions proceed in good yields with amide, carbamate, and sulfonamide nucleophiles, and the optimal catalyst is (DPP)Pd(OCOCF(3))(2) (DPP = 4,7-diphenyl-1,10-phenanthroline). [reaction: see text]

Tetrahydroquinoline skeletons can be formed by a CuCl2-catalyzed one-pot reaction of N-methyl-N-alkylanilines and vinyl ethers in the presence of t-butyl-hydroperoxide.

An efficient and exceptionally mild intramolecular nickel-catalyzed carbon-oxygen bond-forming reaction between vinyl halides and primary, secondary, and tertiary alcohols has been achieved. Zinc powder was found to be an essential additive for obtaining high catalyst turnover and yields. This operationally simple method allows direct access to cyclic vinyl ethers in high yields in a single step.