The present disclosure provides novel methods of making aluminum complexes with utility for promoting epoxide carbonylation reactions. Methods include reacting neutral metal carbonyl compounds with alkylaluminum complexes. For example, a compound of formula I: ##STR00001##
is reacted with a neutral metal carbonyl compound (such as Q′.sub.dM.sub.e(CO).sub.w′) to produce an aluminum-based carbonylation catalyst: ##STR00002##

Methods of preparing fluorinated compounds by carboxylative fluorination using fluoride are contained herein. Fluorinated compounds are provided. Methods of using fluorinated compounds are contained herein.

A catalyst, a preparation method therefor, an electrode containing the catalyst, a membrane-electrode assembly, and a fuel cell are disclosed. The catalyst contains a support; metal particles supported by the support; and a coating layer located on the metal particles, and includes any one selected from the group consisting of phthalocyanine, M-phthalocyanine (wherein M is a transition metal) and a mixture thereof. The catalyst has improved durability since a coating layer is formed on the surface of a commercial catalyst or a conventional catalyst through a relatively easy method without separate treatment. A carbon coating layer formed by post-treating a catalyst including the coating layer further improves durability. Material transfer ability and performance are also improved by a carbon nanofiber or a carbon nanotube generated during post-treatment.

The present invention relates to a transition metal-based heterogeneous carbonylation reaction catalyst that has an excellent catalytic activity and selectivity in the carbonylation reaction and is easily separated from a product, by crosslinking polymerizing a transition metal-based homogeneous catalyst unit through a Friedel-Craft reaction; and a method for preparing lactone using the same. The transition metal-based heterogeneous carbonylation reaction catalyst allows to produce lactone or succinic anhydride with an epoxide compound while showing a high selectivity, and can be applied in industrial very usefully due to easy separation from the product and thus reusing thereof.

A process for preparing a ketone or carboxylic acid by catalytic oxidation of a secondary or primary alcohol comprises adding the secondary or primary alcohol as a raw material and N-hydroxyphthalimide (NHPI) combined with phthalocyanine, serving as a catalytic system, into an amount of an organic solvent into which oxygen gas is then introduced, to proceed with an oxidation reaction to give the ketone or carboxylic acid. The oxygen gas is employed as the source of an oxidant. The oxidation reaction may be carried out under normal pressure at 60 to 120 C. for 9 to 36 hours. The process can produce a high yield of ketone or carboxylic acid. Compared with conventional technology, the process has several advantages, such as the green oxidant, the cheap catalyst which can also be easily prepared and separated, and mild reaction conditions, and it is also an environmentally friendly process for alcohol oxidation.

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.

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.

In one aspect, the disclosure relates to a mode of asymmetric induction in radical processes based on sequential combination of enantiodifferentiative H-atom abstraction and stereoretentive radical substitution. Also disclosed is an asymmetric system for stereoselective synthesis of strained 5-membered cyclic sulfamides via radical 1,5-CH amination of sulfamoyl azides. The disclosed metalloradical system can control the degree and sense of asymmetric induction in the catalytic radical CH amination in a systematic manner. The disclosed system is applicable to a broad scope of substrates with different types of C(sp.sup.3)-H bonds and exhibits reactivity and selectivity, providing access to both enantiomers of useful 5-membered cyclic sulfamides in a highly enantioenriched form. Also disclosed are catalysts useful in these 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.

A polyvinyl alcohol is produced in a method comprising: a polymerization step comprising polymerizing vinyl ester monomers by controlled radical polymerization in the presence of a radical initiator and an organic cobalt complex to obtain a polymer solution containing a polyvinyl ester; an extraction step comprising extracting a cobalt complex from the polymer solution by contacting an aqueous solution containing a water-soluble ligand with the polymer solution; and a saponification step comprising saponifying the polyvinyl ester after the extraction step to obtain a polyvinyl alcohol. A method for producing a polyvinyl alcohol is thus provided that has a narrow molecular weight distribution and a high number-average molecular weight with good hue and further good solubility in water.

The porphyrin-based catalysts for water splitting are composites of porphyrin or metalloporphyrin active ingredients, conductive carbon (e.g., graphene sheets, vapor grown carbon fiber, carbon black, etc.), and a polymer or binder that may be coated on a glassy carbon electrode. The polymer or binder may be Nafion oil or polyvinylidine difluoride. The porphyrin may be a porphyrin having a transition metal or hydrogen at its center, and may be halogenated and/or have a thiophene substituent.