An oxidative homocoupling method of synthesizing certain 2,2-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions: ##STR00001## Associated catalytic systems and compositions are also disclosed.

SiOC-bonded polyether siloxanes are produced by transesterification of alkoxysiloxanes with polyetherols in the presence of trifluoromethanesulfonate as catalyst. The computational total water content of the reactants including alkoxysiloxanes and polyetherols is 5000 ppm by mass, advantageously 300 ppm by mass, preferably 150 ppm by mass, more preferably 100 ppm by mass, in particular 50 ppm by mass. The determination of the individual water contents is performed beforehand, preferably by titration according to Karl Fischer.

Methods and a system for manufacturing a base stock from an ethanol stream are provided. An example method includes dehydrating an ethanol stream to form an impure ethylene stream, recovering an ethylene stream from the impure ethylene stream, and oligomerizing the ethylene stream to form a raw oligomer stream. A light olefinic stream is distilled from the raw oligomer stream and blended with the ethylene stream prior to the oligomerization. A heavy olefinic stream is distilled from the raw oligomer stream and hydro-processed to form a hydro-processed stream. The hydro-processed stream is distilled to form the base stock.

Nanoparticles that can be used as hydrosilylation and dehydrogenative silylation catalysts. The nanoparticles have at least one transition metal with an oxidation state of 0, chosen from the metals of columns 8, 9 and 10 of the periodic table, and at least one carbonyl ligand, preferably a silicide.

Among other things, the present invention encompasses the applicant's recognition that epoxide carbonylation can be performed industrially utilizing syngas streams containing hydrogen, carbon monoxide and varying amounts carbon dioxide. Contrary to expectation, the epoxide carbonylation reaction proceeds selectively in the presence of these mixed gas streams and incorporates excess CO in the syngas stream into valuable chemical precursors, resulting in hydrogen streams substantially free of CO. This is economically and environmentally preferable to performing WSGR which releases the excess carbon as CO2. The integrated processes herein therefore provide improved carbon efficiency for processes based on coal or biomass gasification or steam methane reforming.

Provided are a novel isocyanide compound, a hydrosilylation reaction catalyst having excellent handling properties and storage properties that allows a hydrosilylation reaction to proceed under moderate conditions by using the isocyanide compound, and a method for producing an addition compound by a hydrosilylation reaction using the hydrosilylation reaction catalyst. A hydrosilylation reaction catalyst prepared from a catalyst precursor comprising a transition metal compound of groups 8, 9, or 10 of the periodic table, excluding platinum, such as an iron carboxylate, cobalt carboxylate, or nickel carboxylate, and a ligand comprising an isocyanide compound having an organosiloxane group.

Systems and a method for manufacturing a base stock from a hydrocarbon stream are provided. An example method includes cracking the hydrocarbon stream to form a raw product stream, separating an ethylene stream from the raw product stream, and oligomerizing the ethylene stream to form a raw oligomer stream. A Light olefinic stream is distilled from the raw oligomer stream and oligomerized the light olefinic stream with the ethylene stream. A heavy olefinic stream is distilled from the raw oligomer stream. The heavy olefinic stream is to form a hydro-processed and distilled to form the base stock.

An improved alkaline pretreatment of biomass is provided that uses a homogenous catalyst with one or more metals and metal coordinating ligands, wherein the homogeneous catalyst is used with at least two oxidants in an oxidation reaction to catalytically pretreat lignocellulosic biomass. In one embodiment, hydrogen peroxide and oxygen are utilized as co-oxidants during alkaline-oxidative pretreatment to improve biomass pretreatment and increase enzymatic digestibility. In one embodiment, the homogenous catalyst is copper (II) 2,2-bipyridine (Cu(bpy)). Related methods are also disclosed to improve the economic feasibility of production of lignocellulose derived sugars.

In one aspect, the disclosure relates to a mode of asymmetric induction in radical processes based on enhanced hydrogen-bonding capability and the situation of metal centers in cavity-like chiral environments. Also disclosed is an asymmetric system for stereoselective synthesis of cyclopropane and aziridine derivatives. The disclosed Co(II)-based metalloradical system has been shown to have an unusual capability of controlling both the degree and sense of asymmetric induction in cyclopropanation and aziridination reactions in a systematic manner. The disclosed system is applicable to a broad scope of substrates having diazo or azido moieties and exhibits a remarkable profile of reactivity and selectivity, providing access to cyclopropane diastereomers and aziridine enantiomers in highly enantioenriched forms. Also disclosed are catalysts useful in the disclosed processes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

Surface hydroxyl groups on porous and nonporous metal oxides, such as silica gel and alumina, were metalated with catalyst precursors, such as complexes of earth abundant metals (e.g., Fe, Co, Cr, Ni, Cu, Mn and Mg). The metalated metal oxide catalysts provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of organic transformations. The catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.