Aza-Rubottom Oxidation: Synthetic Access to Primary α-Aminoketones.

An aza analogue of the Rubottom oxidation is reported. This facile transformation takes place at ambient temperature and directly converts silyl enol ethers to the corresponding primary α-aminoketones. The use of hexafluoroisopropanol (HFIP) as the solvent is essential for the success of this reaction. Overall this process is well-suited for the aza-functionalization and derivatization of complex organic molecules.

Cycloaddition reactions of enoldiazo compounds.

Enoldiazo esters and amides have proven to be versatile reagents for cycloaddition reactions that allow highly efficient construction of various carbocycles and heterocycles. Their versatility is exemplified by (1) [2+n]-cycloadditions (n = 3, 4) by the enol silyl ether units of enoldiazo compounds with retention of the diazo functionality to furnish α-cyclic-α-diazo compounds that are themselves subject to further transformations of the diazo functional group; (2) [3+n]-cycloadditions (n = 1-5) by metallo-enolcarbenes formed by catalytic dinitrogen extrusion from enoldiazo compounds; (3) [2+n]-cycloadditions (n = 3, 4) by donor-acceptor cyclopropenes generated in situ from enoldiazo compounds that produce cyclopropane-fused ring systems. The role of dirhodium(ii) and the emergence of copper(i) catalysts are described, as are the different outcomes of reactions initiated with these catalysts. This comprehensive review on cycloaddition reactions of enoldiazo compounds, with emphasis on methodology development, mechanistic insight, and catalyst-controlled chemodivergence, aims to provide inspiration for future discoveries in the field and to catalyze the application of enoldiazo reagents by the wider synthetic community.

Copper-Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides.

Enoldiazoimides, a new subclass of enoldiazo compounds, generate enol-substituted carbonyl ylides whose reactions with sulfur ylides enable an unprecedented formal [4+2] cycloaddition. The resulting multifunctionalized indolizidinones, which incorporate sulfur, are formed in good yields under mild reaction conditions. The uniqueness of this transformation stems from the role of the silyl-protected enol, since the corresponding acetyldiazoimide failed to provide any cross-products in metal-catalyzed reactions with sulfur ylides. This copper-catalyzed cycloaddition is initiated with the generation of enol-substituted carbonyl ylides and sulfur ylides from enoldiazoimides and sulfonium salts, respectively, and proceeds through stepwise six-membered ring formation, C-O and C-S bond cleavage, and silyl and acetyl group migration.

Divergent Rhodium-Catalyzed Cyclization Reactions of Enoldiazoacetamides with Nitrosoarenes.

The first cyclization reactions of enoldiazo compounds with nitrosoarenes have been developed. Under the catalysis of rhodium(II) octanoate, [3 + 2]-cyclization between enoldiazoacetamides and nitrosoarenes occurred through cleavages of the enol double bond and the amide bond, thus furnishing fully substituted 5-isoxazolone derivatives. Upon changing the catalyst to rhodium(II) caprolactamate, the reaction pathway switched to an unprecedented formal [5 + 1]-cyclization that provided multifunctionalized 1,3-oxazin-4-ones with near exclusivity under otherwise identical conditions. Mechanistic studies uncovered distinct catalytic activities and reaction intermediates, which plausibly rationalized the novel reactivity and catalyst-controlled chemodivergence. Furthermore, a mechanism-inspired enantioselective rhodium-catalyzed reaction of γ-substituted enoldiazoacetamide with nitrosobenzene produced highly enantioenriched heterocycle-linked trialkylamine.

Copper-Catalyzed Divergent Addition Reactions of Enoldiazoacetamides with Nitrones.

Catalyst-controlled divergent addition reactions of enoldiazoacetamides with nitrones have been developed. By using copper(I) tetrafluoroborate/bisoxazoline complex as the catalyst, a [3+3]-cycloaddition reaction was achieved with excellent yield and enantioselectivity under exceptionally mild conditions, which represents the first highly enantioselective base-metal-catalyzed vinylcarbene transformation. When the catalyst was changed to copper(I) triflate, Mannich addition products were formed in high yields with near exclusivity under otherwise identical conditions.

Dirhodium(II)-Catalyzed Annulation of Enoldiazoacetamides with α-Diazoketones: An Efficient and Highly Selective Approach to Fused and Bridged Ring Systems.

A dirhodium(II)-catalyzed annulation reaction between two structurally different diazocarbonyl compounds furnishes the donor-acceptor cyclopropane-fused benzoxa[3.2.1]octane scaffold with excellent chemo-, regio-, and diastereoselectivity under exceptionally mild conditions. The composite transformation occurs by [3+2]-cycloaddition between donor-acceptor cyclopropenes generated from enoldiazoacetamides and carbonyl ylides formed from intramolecular carbene-carbonyl cyclization in one pot with one catalyst. The annulation products can be readily transformed into benzoxa[3.3.1]nonane and hexahydronaphthofuran derivatives with exact stereocontrol. This method allows the efficient construction of three fused and bridged ring systems, all of which are important skeletons of numerous biologically active natural products.

Copper-catalyzed B-H bond insertion reaction: a highly efficient and enantioselective C-B bond-forming reaction with amine-borane and phosphine-borane adducts.

A copper-catalyzed B-H bond insertion reaction with amine- and phosphine-borane adducts was realized with high yield and enantioselectivity under mild reaction conditions. The B-H bond insertion reaction provides a new C-B bond-forming methodology and an efficient approach to chiral organoboron compounds.

Phosphorus fluoride exchange: Multidimensional catalytic click chemistry from phosphorus connective hubs.

Phosphorus Fluoride Exchange (PFEx) represents a cutting-edge advancement in catalytic click-reaction technology. Drawing inspiration from Nature's phosphate connectors, PFEx facilitates the reliable coupling of P(V)-F loaded hubs with aryl alcohols, alkyl alcohols, and amines to produce stable, multidimensional P(V)-O and P(V)-N linked products. The rate of P-F exchange is significantly enhanced by Lewis amine base catalysis, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). PFEx substrates containing multiple P-F bonds are capable of selective, serial exchange reactions via judicious catalyst selection. In fewer than four synthetic steps, controlled projections can be deliberately incorporated along three of the four tetrahedral axes departing from the P(V) central hub, thus taking full advantage of the potential for generating three-dimensional diversity. Furthermore, late-stage functionalization of drugs and drug fragments can be achieved with the polyvalent PFEx hub, hexafluorocyclotriphosphazene (HFP), as has been demonstrated in prior research.

A biomimetic chitosan derivates: preparation, characterization and transdermal enhancement studies of N-arginine chitosan.

A novel arginine-rich chitosan (CS) derivates mimicked cell penetration peptides; N-Arginine chitosan (N-Arg-CS) was prepared by two reaction methods involving activated L-arginine and the amine group on the chitosan. FTIR spectra showed that arginine was chemically coupled with CS. Elemental analysis estimated that the degrees of substitution (DS) of arginine in CS were 6%, 31.3% and 61.5%, respectively. The drug adefovir was chosen as model and its permeation flux across excised mice skin was investigated using a Franz diffusion cell. The results showed that the most effective enhancer was 2% (w/v) concentration of 10 kDa N-Arg-CS with 6% DS. At neutral pH, the cumulative amount of adefovir permeated after 12 hours was 2.63 ± 0.19 mg cm(-2) which was 5.83-fold more than adefovir aqueous solution. Meanwhile N-Arg-CS was 1.83, 2.22, and 2.45 times more effective than Azone, eucalyptus and peppermint, respectively. The obtained results suggest that N-Arg-CS could be a promising transdermal enhancer.

Topological quantum phase transitions of Chern insulators in disk geometry.

We investigate topological quantum phase transitions (TQPTs) of Chern insulators in two-dimensional honeycomb-lattice disk with six-fold rotational symmetry. By considering the nearest-neighbor, next-nearest-neighbor hopping parameters and the staggered-flux parameter of the Haldane model, we can obtain rich topological quantum phases. The trivial and non-trivial phases of the Haldane model in disk geometry can be distinguished based on chiral edge states, real-space particle densities and local density of states. We also explore the TQPTs of Chern insulators with an external potential which varies with the radius of the disk geometry. Some interesting topological phases with large Chern numbers can be observed when we consider long-distance hoppings. Furthermore, we use a machine learning algorithm as an effective way to automatically identify various topological phases and phase diagrams for the Haldane model in disk geometry.

Highly effective electrosynthesis of hydrogen peroxide from oxygen on a redox-active cationic covalent triazine network.

Direct electrosynthesis of hydrogen peroxide (H2O2) by oxygen reduction is a green and safe strategy to replace the traditional anthraquinone process. Herein, we have designed a two-dimensional redox-active cationic covalent triazine network to be used directly as a cost-effective metal-free electrocatalyst for the oxygen reduction reaction (ORR) to form H2O2. Such a dicationic 2D polymer possesses a porous structure with pore diameters of 2-10 nm and a total N content of 13.3 wt%. The electron paramagnetic resonance experiment confirms the reduction of a viologen-based polymer to radical cations and the subsequent generation of superoxygen radicals. The radical characteristics and high N content within this polymer are the essential for the efficient ORR via a two-electron pathway. As a result, the present electrocatalyst exhibits a high ORR activity and excellent H2O2 selectivity (∼85%), thus providing a feasible possibility of designing highly selective metal-free electrocatalysts for electrocatalytic production of H2O2 from O2.

Highly Regio- and Enantioselective Formal [3 + 2]-Annulation of Indoles with Electrophilic Enol Carbene Intermediates.

Chiral cyclopentane-fused indolines are synthesized with high regio- and enantiocontrol by formal [3 + 2]-annulation reactions of indoles and electrophilic enol carbenes. High enantioselectivity and exclusive regiocontrol occurred with enoldiazoacetamides using a less sterically encumbered prolinate-ligated dirhodium(II) catalyst in reactions with N-substituted indoles without substituents at the 2- or 3-positions via a selective vinylogous addition process. In this transformation, donor-acceptor cyclopropenes generated from enoldiazoacetamides serve as the carbene precursors to form metal carbene intermediates.

Lewis Acid/Rhodium-Catalyzed Formal [3 + 3]-Cycloaddition of Enoldiazoacetates with Donor-Acceptor Cyclopropanes.

A formal [3 + 3]-cycloaddition of enoldiazoacetates with donor-acceptor cyclopropanes was realized by the combination of a Lewis acid-catalyzed diastereoselective [3 + 2]-cycloaddition and a subsequent rhodium-catalyzed chemoselective ring expansion. This tandem transformation provides an efficient approach to highly functionalized cyclohexenes.

[Macrobenthic community structure and bioassessment for water quality of Banqiao Reservoir in Huaihe River basin].

In order to demonstrate macrobenthic community structure dynamics and conduct a biological evaluation of water quality in Banqiao Reservoir, we collected seasonal samples from January to November 2014 across 15 sampling sites. A total of 17 species belonging to five families, four classes, and 3 phyla were identified, including 8 chironomidae, 4 oligochaeta and 5 mollusc. Bellamya aeruginosa, Corbicula fluminea, Branchiura sowerbyi, Pelopia sp. and Glyptotendipes sp. were the important species in Banqiao Reservoir. The total density, biomass and biodiversity of marobenthos showed significant spatial and temporal differences. ANOSIM analysis indicated that the macrobenthic community structure also differed significantly among regions and seasons, and the main contributing species were Glyptotendipes sp., Pelopia sp. and B. sowerbyi. The abundance-biomass comparison curves (ABC curves) indicated that the current macrobenthic community in Banqiao Reservoir was stable. Combined with the biodiversity index, biological pollution index (BPI) and Hilsenhoff biotic index (BI), it was suggested that Banqiao Reservoir suffered slight pollution.