Hans Adolfsson

Catalytic amide formation from non-activated carboxylic acids and amines

The amide functionality is found in a wide variety of biological and synthetic structures such as proteins, polymers, pesticides and pharmaceuticals. Due to the fact that synthetic amides are still mainly produced by the aid of coupling reagents with poor atom-economy, the direct catalytic formation of amides from carboxylic acids and amines has become a field of emerging importance. A general, efficient and selective catalytic method for this transformation would meet well with the increasing demands for green chemistry procedures. This review covers catalytic and synthetically relevant methods for direct condensation of carboxylic acids and amines. A comprehensive overview of homogeneous and heterogeneous catalytic methods is presented, covering biocatalysts, Lewis acid catalysts based on boron and metals as well an assortment of other types of catalysts.

Chiral quinuclidine-based amine catalysts for the asymmetric one-pot, three-component aza-Baylis–Hillman reaction

Chiral quinuclidine-based amine catalysts for the asymmetric one-pot, three-component aza-Baylis–Hillman reaction

Comparison of amine additives most effective in the new methyltrioxorhenium-catalyzed epoxidation process

Abstract Three different heterocyclic amine additives, pyridine, 3-cyanopyridine and pyrazole are compared in the methyltrioxorhenium (MTO) catalyzed epoxidation of olefins using aqueous hydrogen peroxide.

Direct Amide Coupling of Non-activated Carboxylic Acids and Amines Catalysed by Zirconium(IV) Chloride

Direct Amide Coupling of Non-activated Carboxylic Acids and Amines Catalysed by Zirconium(IV) Chloride

Metal-Free N-Arylation of Secondary Amides at Room Temperature

The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

Mechanistic investigations into the asymmetric transfer hydrogenation of ketones catalyzed by pseudo-dipeptide ruthenium complexes.

The combination of N-Boc-protected alpha-amino acid hydroxyamides (pseudo-dipeptides) and [{Ru(p-cymene)Cl(2)}(2)] resulted in the formation of superior catalysts for the asymmetric transfer hydrogenation (ATH) of non-activated aryl alkyl ketones in propan-2-ol. The overall kinetics of the ATH of acetophenone to form 1-phenylethanol in the presence of ruthenium pseudo-dipeptide catalysts were studied, and the individual rate constants for the processes were determined. Addition of lithium chloride to the reaction mixtures had a strong influence on the rates and selectivities of the processes. Kinetic isotope effects (KIEs) for the reduction were determined and the results clearly show that the hydride transfer is rate-determining, whereas no KIEs were detected for the proton transfer. From these observations a novel bimetallic outer-sphere-type mechanism for these ATH process is proposed, in which the bifunctional catalysts mediate the transfer of a hydride and an alkali metal ion between the hydrogen donor and the substrate. Furthermore, the use of a mixture of propan-2-ol and THF (1:1) proved to enhance the rates of the ATH reactions. A series of aryl alkyl ketones were reduced under these conditions in the presence of 0.5 mol % of catalyst, and the corresponding secondary alcohols were formed in high yields and with excellent enantioselectivities (>99% ee) in short reaction times.

C3-symmetric tripodal tetra-amines—preparation from chiral amino alcohols via aziridines

Abstract Enantiopure N -sulfonylaziridines, conveniently obtained from readily available enantiopure amino alcohols, undergo smooth ring opening reactions using ammonia as a nucleophile to yield tripodal tetradentate C 3 -symmetric amines. N -alkylation and subsequent removal of the sulfonyl groups provide access to alkyl-substituted analogs.

Novel simple and highly modular ligands for efficient asymmetric transfer-hydrogenation of ketones

Novel simple and highly modular dipeptide-analogue ligands combined with [RuCl2(p-cymene)]2 were demonstrated to efficiently catalyze the reduction of ketones under hydrogen transfer conditions with enantioselectivities up to 96%.

A simple and efficient method for the preparation of pyridine-N-oxides II

Abstract Oxidation of pyridines with bis(trimethylsilyl)peroxide in the presence of catalytic amounts of inorganic rhenium derivatives gives high yields of their analytically pure N-oxides by simple work-ups, typically a filtration or a Kugelrohr distillation.

Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Amino Acid Derived Rhodium Complexes: On the Origin of Enantioselectivity and Enantioswitchability

Amino acid based thioamides, hydroxamic acids, and hydrazides have been evaluated as ligands in the rhodium-catalyzed asymmetric transfer hydrogenation of ketones in 2-propanol. Catalysts containing thioamide ligands derived from L-valine were found to selectively generate the product with an R configuration (95 % ee), whereas the corresponding L-valine-based hydroxamic acids or hydrazides facilitated the formation of the (S)-alcohols (97 and 91 % ee, respectively). The catalytic reduction was examined by performing a structure-activity correlation investigation with differently functionalized or substituted ligands and the results obtained indicate that the major difference between the thioamide and hydroxamic acid based catalysts is the coordination mode of the ligands. Kinetic experiments were performed and the rate constants for the reduction reactions were determined by using rhodium-arene catalysts derived from amino acid thioamide and hydroxamic acid ligands. The data obtained show that the thioamide-based catalyst systems demonstrate a pseudo-first-order dependence on the substrate, whereas pseudo-zero-order dependence was observed for the hydroxamic acid containing catalysts. Furthermore, the kinetic experiments revealed that the rate-limiting steps of the two catalytic systems differ. From the data obtained in the structure-activity correlation investigation and along with the kinetic investigation it was concluded that the enantioswitchable nature of the catalysts studied originates from different ligand coordination, which affects the rate-limiting step of the catalytic reduction reaction.