Density functional theory calculations demonstrate that Al(III)-catalyzed conversion of glyoxal to glycolic acid proceeds via a 7-membered dual Lewis acid-hydrogen bonding activation transition state of the 1,2-hydride shift, rather than the previously proposed 5-membered metal-alkoxide chelate activation transition state.

An unusual [1,5]-Brook rearrangement of the lithium alkoxide of geminal bis(silyl) homoallylic alcohol is described. The unique steric and electronic effects of geminal bis(silane) were found to be crucial for promoting this long-range silyl migration, as well as for facilitating the subsequent γ/Z-selective addition of silyl allyllithium with carbonyl compounds to synthesize diverse configurat...

This work introduces the novel use of a highly stable UiO-66-NH2 in water with linker release less than 0.2‰ (per-mile) wide pH range. The MOF was prepared by fast microwave-assisted method comparing for first time effect two Zr precursors: oxychloride and organic alkoxide; synthesis temperatures 120–180 ºC. as precursor led to bigger particle crystal size alkoxide. sample ZrOCl2 at 140 ºC resu...

The combination of a boronic acid and a Lewis base, both employed in substoichiometric amounts, enables the regioselective silylation of cis-diol groups in alkylpyranoside substrates. The proposed mode of activation involves the formation of a tetracoordinate adduct that displays enhanced nucleophilicity at the boron-bound alkoxide groups.

Trinuclear complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) were synthesized using a ligand architecture based upon a 1,3,5-triarylbenzene core decorated with six pyridines and three alkoxide moieties. Characterization via X-ray diffraction, NMR, and magnetism studies is discussed.

Homopropargylic alcohols undergo directed hydrozirconation with Schwartz reagent (Cp(2)ZrHCl) to generate vinyl-metal species in which the metal fragment is proximal to the alkoxide. Electrophilic trapping yields tri-substituted olefins in good yields with good control of regio- and stereochemistry. Experiments with a homopropargylic ether confirmed the role of the hydroxyl group in the directe...

Selective oxidation of alcohol in water using molecular oxygen as the terminal oxidant is mediated by rhodium porphyrin complexes. Addition of methanol to an aqueous solution of (TSPP)Rh(III) resulted in observation of the key intermediate porphyrin rhodium(III) methoxide species. The activation parameters for betaC-H elimination of Rh-alkoxide were evaluated.