Laboratory for Advanced Materials and New Catalysis, School of Chemistry and Materials Science, Hubei University, Wuhan 430062, China,Laboratory of Natural Gas Utilization and Applied Catalysis, Dalian Institute of Chemical Physics of Chinese Academy of Sciences, Dalian 116023,China, and Jingmen Technological College, Jingmen 448000, ChinaReceived June 30, 2004

Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation

Polymer-Supported Organic Catalysts†

This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

Nitroxides: applications in synthesis and in polymer chemistry.

Free radical functionalization of organic compounds catalyzed by N-hydroxyphthalimide.

Asymmetric catalysis mediated by synthetic peptides.

Selective catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide: a coproduct-free route to phenol

The invention relates to a method for the production of phenol derivatives by performing catalytic oxidation of an aromatic hydrocarbon to obtain a hydroperoxide and subsequently cleaving the hydroperoxide into a phenol derivative and a ketone in the presence of a radical starter, wherein a compound of formula (I) is used as oxidation catalyst, wherein R1, R2 = H, an aliphatic or aromatic alkoxy radical, a carboxyl radical, an alkoxycarbonyl radical or a hydrocarbon radical, with 1 to 20 carbon atoms, SO?3?H, NH2, OH, F, Cl, Br, I and/or NO2, wherein R?1 and R2? represent identical or different radicals or R?1 and R2? may be linked to one another by a covalent bond, wherein X, Z = C, S, CH?2;? Y = O, OH; k = 0, 1, 2; l = 0, 1, 2 and m = 1 to 3; wherein the molar ratio between the catalyst and the aromatic hydrocarbon is less than 10 mol %.

Method for producing aromatic alcohols, especially phenol

The invention relates to a method for oxidizing substrates such as hydrocarbons, waxes or soot. The method involves the use of a compound of formula (I) in which: R?1 and R2? represent H, an aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each having 1 to 20 hydrocarbon atoms, SO?3?H, NH2, OH, F, Cl, Br, I and/or NO2, whereby R?1 and R2? designate identical or different radicals or R?1 and R2? can be linked to one another via a covalent bonding; Q?1? and Q2 represent C, CH, N, CR?5?, each being the same or different; X and Z represent C, S, CH?2?, each being the same or different; Y represents O and OH; k = 0, 1, 2; l = 0, 1, 2; m = 1 to 3, and; R?5? represents one of the meanings of R1. Said compound is used as a catalyst in the presence of a radical initiator, whereby the molar ratio of the catalyst to the hydrocarbon is less than 10 mol %. Peroxy compounds or azo compounds can be used as the radical initiator. Preferred substrates are aliphatic or aromatic hydrocarbons.

Method for oxidizing hydrocarbons

Two novel soluble polymer-bound oligo-L-leucines 2 and 5, which can be retained by a membrane reactor system, have been prepared and used as catalysts for the continuously operated asymmetric epoxidation of chalcone. The optimized batch reaction conditions yield epoxychalcone in high enantioselectivities (up to 94%) and conversions (over 99%) after 15 minutes.

Juliá-Colonna Asymmetric Epoxidation in a Continuously Operated Chemzyme Membrane Reactor

The invention relates to a method for producing functionalised oligomeric silsesquioxanes by reacting partially condensed oligomeric silsesquioxanes with alkoxysilanes. The invention also relates to the use of the same for further derivatisations, for the synthesis of catalysts and the starting compounds thereof, and for the synthesis and modification of polymers.

Adolf Kühnle

Papers

Selective catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide: a coproduct-free route to phenol

Method for producing aromatic alcohols, especially phenol

Method for oxidizing hydrocarbons

Juliá-Colonna Asymmetric Epoxidation in a Continuously Operated Chemzyme Membrane Reactor

Method for producing functionalised oligomeric silsesquioxanes and the use of the same