Recent Uses of ,-Dimethylformamide and ,-Dimethylacetamide as Reagents.

,-Dimethylformamide and ,-dimethylacetamide are multipurpose reagents which deliver their own H, C, N and O atoms for the synthesis of a variety of compounds under a number of different experimental conditions. The review mainly highlights the corresponding literature published over the last years.

Palladium-catalysed inter- and intramolecular formation of C-O bonds from allenes.

The Pd-catalysed formation of a C-O bond from allenes mainly occurs via the inter- or intramolecular reaction with a hydroxyl group belonging to an alcohol, a phenol or an acid. A carbonyl or a carbonate entity can also be involved. In most cases, the formation of the C-O bond is one step of a domino reaction leading also to a C-C or C-N bond, or to another C-O bond.

Nanocrystalline starch grafted palladium(II) complex for the Mizoroki-Heck reaction.

Nanocrystalline starch produced from the acid hydrolysis of gelatinized starch has been used for the first time to support palladium(II) ethylenediamine complex. The nanocrystalline starch supported Pd(II) complex was found to be an efficient and efficiently recycled catalyst for the Mizoroki-Heck reaction of furans and thiophenes with styrenes under mild reaction conditions.

ESI-MS studies of the dehydrogenative Heck reaction of furans with acrylates using benzoquinone as the reoxidant and DMSO as the solvent.

Electrospray ionization mass spectrometry, subsequent MS/MS, and high-resolution mass spectrometry were used to study the dehydrogenative Heck reaction of 2-alkylfurans 1 with acrylates 2, using [Pd(OAc)(2)](3) as the precatalyst, benzoquinone (BQ) as the stoichiometric oxidant, and a mixture of DMSO and AcOH as the solvent. Complexation of [Pd(OAc)(2)](3) by DMSO afforded mononuclear and dinuclear Pd(II) species, which proved to be active catalysts for the C-H activation of 1. Mononuclear and dinuclear Pd(II) species seem also to be involved in the insertion of 2 into the furyl-Pd bond.

Acidic pretreatment of wheat straw in decanol for the production of surfactant, lignin and glucose.

Wheat straw is an abundant residue of agriculture which is increasingly being considered as feedstock for the production of fuels, energy and chemicals. The acidic decanol-based pre-treatment of wheat straw has been investigated in this work. Wheat straw hemicellulose has been efficiently converted during a single step operation into decyl pentoside surfactants and the remaining material has been preserved keeping all its promises as potential feedstock for fuels or value added platform chemicals such as hydroxymethylfurfural (HMF).

Direct conversion of xylan into alkyl pentosides.

Xylan has been used as a raw material in the synthesis of butyl, octyl and decyl glycosides. Mixtures of D-xylose-, L-arabinose- and D-glucose-based surfactants were obtained under smooth conditions with high yields in a one-pot process. The surface activities of octyl and decyl glycosides thus obtained have been studied and compared with that of pure alkyl D-xylosides.

Low catalyst loadings for the production of carboxylic acids from polysaccharides and hydrogen peroxide.

The oxidation of starch, xylans, potato flesh and wheat flour by H(2)O(2), in the presence of MSO(4) (M=Cu, Fe) as catalyst, led to depolymerization, and formation of solutions containing polyhydroxycarboxylic acids. Some of these oxidized compounds facilitate the process, leading to efficient transformations even with very low amounts of catalyst.

Palladium-catalyzed allylic acyloxylation of terminal alkenes in the presence of a base.

The efficiency and the selectivity of the Pd-catalyzed oxidation, in carboxylic acids, of terminal alkenes are strongly improved in the presence of a base. The methodology is particularly well adapted for the oxidation of homoallylic alcohols, for which the resulting acyloxylated products are obtained selectively as E-isomers in fair to good yields.

Palladium-catalyzed dehydrogenative coupling of furans with styrenes.

Under palladium(II)-catalyzed and oxidative conditions, the coupling of furans with styrenes leads to the formation of Heck-type products in medium to good yields. The reaction is highly regio- and stereoselective, giving trans-olefins predominantly.

Copper(I)-catalyzed synthesis of substituted 2-mercapto benzimidazoles.

An efficient method for the preparation of various substituted 2-mercapto benzimidazoles from their corresponding thioureas has been developed. S-alkylation of thioureas followed by Cu-catalyzed intramolecular N-arylation furnished substituted 2-mercapto benzimidazoles in high yields and short reaction times. Furthermore, 2-mercapto benzimidazoles substituted with a p-methoxybenzyl group allowed access to benzimidazole thiones.

Mechanistic insights into the palladiumII-catalyzed hydroxyalkoxylation of 2-allylphenols.

The Pd(OCOCF3)2/[(HOCH2CH2NHCOCH2)2NCH2]2-catalyzed oxidation of o-allylphenol with H2O2 in water/methanol affords a syn and anti mixture of 2-(1,2-dihydroxypropyl)phenol and 2-(2-hydroxy-1-methoxypropyl)phenol. Mechanistic experiments and ESI-MS studies support a pathway wherein isomerization of the C=C bond followed by its epoxidation and oxirane opening led to the products. Recycling of the catalytic system led to gradual lost of activity.

Taming reactive phenol tautomers and o-quinone methides with transition metals: a structure-reactivity relationship.

Quinone methides act as important intermediates in organic syntheses, as well as in chemical and biological processes; however, examples of such isolated species are scarce as a result of their high reactivity. Phenol tautomers (keto form of phenol) are also important intermediates in several organic and organometallic reactions; nevertheless, isolated complexes are rare. This Account reviews the recent progress on the synthesis and reactivity of iridium and rhodium o-quinone methide complexes as well as on iridium-mediated ortho functionalization of phenols.