N-Substituted aromatic and heteroaromatic amides reacted with substituted allylic alcohols in the presence of a ruthenium catalyst, AgSbF6 and a Cu(OAc)2·H2O oxidant, affording 3-substituted isoindolinone derivatives with diverse substituents in good to excellent yields. A possible reaction mechanism involving a five-membered ruthenacycle intermediate was proposed and strongly supported by expe...

A novel visible light promoted carbodifluoroalkylation of allylic alcohols is disclosed. A series of difluoro 1,5-dicarbonyl compounds were obtained through a tandem radical addition and 1,2-aryl migration process. Mechanistic analysis indicated that the 1,2-aryl rearrangement proceeded via a radical intermediate.

An overview of the synthesis and applications of chiral 2,3-epoxy alcohols containing unsaturated chains is presented. One of the fundamental synthetic routes to these compounds is Sharpless asymmetric epoxidation, which is reliable, highly chemoselective and enables easy prediction of the product enantioselectivity. Thus, unsaturated epoxy alcohols are readily obtained by selective oxidation o...

The influence of catalyst components in the copper-TEMPO (2,2,6,6-tetramethylpiperidine N-oxide) catalysed aerobic oxidation of alcohols was investigated. The type and amount of base greatly influences reactivity. The bipyridyl ligand concentration had no major influence on catalysis, but excessive amounts led to a decrease in activity for longer reaction times. The kinetic dependency for TEMPO...

The catalytic asymmetric synthesis of tertiary alcohols by the addition of organometallic reagents to ketones is of central importance in organic chemistry. The resulting quaternary stereocentres are difficult to prepare selectively by other means despite their widespread occurrence in natural products and pharmaceuticals. Here we report on a new methodology which allows access to both α-bromo-...

The efficiency and selectivity of hydrogen atom transfer from organic molecules are often difficult to control in the presence of multiple potential hydrogen atom donors and acceptors. Here, we describe the mechanistic evaluation of a mode of catalytic activation that accomplishes the highly selective photoredox α-alkylation/lactonization of alcohols with methyl acrylate via a hydrogen atom tra...

A novel SBA-15-functionalized TEMPO confined ionic liquid [BMIm]Br was found to be a highly efficient and recyclable catalyst system for the transition-metal-free aerobic oxidation of a wide range of structurally diverse alcohols. Thanks to the strong physical confinement of the ionic liquid inside the mesochannels of SBA-15-supported TEMPO, the resulting solid catalyst showed improved selectiv...

The cationic ruthenium catalyst generated upon the acid-base reaction of H2Ru(CO)(PPh3)3 and 2,4,6-(2-Pr)3PhSO3H promotes the redox-triggered C-C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, alo...

Gold catalysts display high activity and good selectivity for partial oxidation of a number of alcohol species. In this work, we discuss the effects of oxygen adatoms and surface hydroxyls on the selectivity for oxidation of allylic alcohols (allyl alcohol and crotyl alcohol) on gold surfaces. Utilizing temperature programmed desorption (TPD), reactive molecular beam scattering (RMBS), and dens...

A highly efficient site-selective desymmetric mono-hydrogenation of 1,4-dienes is reported. This protocol allows rapid access to a wide range chiral allylic alcohols and amides bearing two vicinal centers adjacent the alkene. The utility this method further highlighted by synthesis alkyl side chain zaragozic acid formal total (+)-invictolide.