A High-Valent Non-Heme μ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen

This study deals with the unprecedented reactivity of dinuclear non-heme Mn^II–thiolate complexes with O₂, which dependent on the protonation state of the initial Mn^II dimer selectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo Mn^IV complex. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled ¹⁸O₂ unambiguously show that the oxygen atoms present in the Mn^IV dimers originate from O₂. Based on experimental observations and DFT calculations, evidence is provided that these Mn^IV species comproportionate with a Mn^II precursor to yield μ-oxo and/or μ-hydroxo Mn^III dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non-heme high-valent μ-oxo and μ-hydroxo Mn species from Mn^II precursors and O₂.     

Determination of Immunoglobulin G by a Hemin–Manganese(IV) Oxide-Labeled Enzyme-linked Immunosorbent Assay

An enzyme-linked immunosorbent assay (ELISA) is reported for human immunoglobulin G based on synthesized hemin–MnO₂ nanocomposite as the label. Enhanced sensitivity was obtained due to the increased catalytic activity of the hemin–MnO₂ nanocomposite toward 3,3′,5,5′-tetramethylbenzidine compared to hemin and MnO₂ alone. The synthesized hemin–MnO₂ nanocomposite was characterized by transmission electron microscopy and its catalytic activity to 3,3′,5,5′-tetramethylbenzidine was investigated by ultraviolet–visible absorption spectroscopy. After assembly of the sandwich-type immunoassay in the 96 wells of the plate the hemin–MnO₂-based label catalyzed 3,3′,5,5′-tetramethylbenzidine into blue compounds that were monitored by a plate reader. The absorbance increased with the concentration of human immunoglobulin G. The immunoassay displayed high sensitivity, a long linear dynamic range, and good selectivity for human immunoglobulin G. The immunoassay was also used for the determination of human immunoglobulin G in serum with favorable results. The developed assay combines the high throughput and low cost of ELISA with the simplicity of nanocomposite labeling and is suitable for application in clinical diagnosis.     

Direct Aroylation of Olefins through a Cobalt/Photoredox-Catalyzed Decarboxylative and Dehydrogenative Coupling with α-Oxo Acids

A photoredox/cobalt dual catalytic procedure has been developed that allows benzoylation of olefins. Here the photoredox catalyst effects the decarboxylation of α-ketoacids to form benzoyl radicals. After addition of this radical to styrenes, the cobalt catalyst abstracts a H-atom. Hydrogen evolution from the putative cobalt hydride intermediate allows a Heck-like aroylation without the need for a stoichiometric oxidant. Mechanistic studies reveal that electronically different styrenes lead to a curved Hammett plot, thus suggesting a change in product-determining step in the catalytic mechanism.     

Sustainable Synthesis of α-Hydroxycarboxylic Acids by Manganese Catalyzed Acceptorless Dehydrogenative Coupling of Ethylene Glycol and Primary Alcohols**

Herein, we report a straightforward synthesis of valuable α-hydroxycarboxylic acid molecules via an acceptorless dehydrogenative coupling of ethylene glycol and primary alcohols. A bench-stable manganese complex catalyzed the reaction, which is scalable, with the product being isolated with high yields and selectivities under mild conditions. The protocol is environmentally benign, producing water and hydrogen gas as the only byproducts. Methanol can also be used as a C1 source for producing the platform molecule lactic acid, with a high turnover of >10⁴. The methodology was also used to functionalize alcohols derived from natural products and fatty acids. Furthermore, it was applied for synthesizing α-amino acid, α-thiocarboxylic acid, and several drugs and bioactive molecules, including endogenous metabolites, Danshensu, Enalapril, Lisinopril, and Rosmarinic acid. Preliminary mechanistic studies were performed to shed light on the mechanism involved in the reaction.     

Sulfamic Acid as a Cost-effective Catalyst for Acetolysis of Cyclic Ethers

Sulfamic acid has been used as an efficient catalyst and green alternative for conventional acidic materials to promote the acetolysis reaction of THF to produce 1,4-diacetoxybutane. This method is also applicable in the acetolysis of other cyclic ethers, such as methyl substituted THF and tetrahydropyran and 1,4-dioxane which is less reactivity.     

Reaction of Olefins with Sulfuryl Chloride and Cyclic Ethers: An Efficient Synthesis of α-Chloroalkyl ω-Chloroalkyl Ethers

Olefins react with sulfuryl chloride in presence of cyclic ethers to form the corresponding α-chloroalkyl ω-chloroalkyl ethers     

Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

A mixed-valence dinuclear manganese complex, [MnⅡMnⅢL](ClO4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P21/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N3O3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.     

Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes

An oxidative strategy is reported to access α-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C−H bonds in the absence of the Thorpe–Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F−C alkylations. This chemistry provides rapid access to structurally diverse α-BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron-donating group that attenuates the high electrophilicity of the gold carbene center.     

Easy Conversion of Dimethyl α-(Bromomethyl)fumarate into Functionalized Allyl Ethers Mediated by DABCO

New functionalized allyl ethers were obtained in good yields following the mild selective reaction of different alcohols with allyl bromide in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) and a catalytic amount of triethylamine (TEA) at room temperature.     

γ-Oxygenation of α,β-unsaturated esters by vinylogous O-nitroso Mukaiyama aldol reaction

A practical procedure has been developed for γ-oxygenation of α,β-unsaturated esters by a vinylogous O-nitroso Mukaiyama aldol reaction followed by a one-pot N-O bond heterolysis of the in situ generated γ-aminoxy-α,β-unsaturated esters.     

Copper(II) and oxovanadium(IV) complexes of α-hydroxymethylserine

Summary Potentiometric and spectroscopic measurements were used to characterize the binding ability of -hydroxy-methylserine (Hms) with copper(II) and oxovanadium(IV) ions. The ligand was found to be generally a more efficient chelating agent than serine. Both of the deprotonated hydroxyl groups of Hms can be involved in coordination to vanadyl ions, whereas copper(II) binds in the same way as with serine.     

Enantioselective Hydrogenation of α,β-Unsaturated Cyclic Ketones by Double Asymmetric Induction Preparation of (R)-Muscone

(R)-Muscone[(R)-6]isanodoriferouscomPoundisolatedfromthemalemuskdeer.BecauseofthenatUralsupplyisseverelylbotofanumberofSyntheticmethodshaveaPPearedintheliteratUre['].However,eachofthepublishedenahoselechveopthehcprocessessuffersfromoneormoreofthefollowingflollgandcomplicatedprocess,lowcheforcalandophcalvields,andscarcityofstartingmaterials[2].Inl98o,TrostetaldeveloPedashortprocesstoopthesize(dl)-musconeingoodcheforca1yteld,andthestartinmaterialiseasil3'a.ailablef3];Ouradriistoobtain(R)-mu…     

Determination of Sterically Hindered Phenols and α-Tocopherol by Cyclic Voltammetry

Sterically hindered phenols (2,6-di-tert-butyl-4-methylphenol (BHT) and its derivatives) are irreversibly oxidized at +0.96–1.30 V on glassy carbon electrode (GCE) in 0.1 M LiCIO₄ in acetonitrile in accordance to cyclic voltammetry data. α-Tocopherol gives oxidation step at +0.4 V on voltammograms under the same conditions. Oxidation process leads to formation of corresponding quinoid derivatives. Calibration graphs linearity is 1.5–2 order for all compounds under investigation. Limits of detection are in the range 9.6–44.3 µM. The approach has been applied for determination of BHT and α-tocopherol in vegetable and lubricating oils as well as pharmaceuticals and cosmetics using preliminary single extraction of analytes with acetonitrile for 15 min at oil/extractant ratio of 1:2.5.     

Reactions of Dicarbonyl(η5-Cyclopentadienyl)Iron(II)-Complexes of Two Cyclic Enol Ethers with Selected Nucleophiles

Dicarbonyl(η⁵-cyclopentadienyl)iron(II)-complexes of 2,3-dihydrofuran and 3,4-dihydro-2H-pyran rapidly react with carbanionic nucleophiles. The adducts of certain nucleophiles, such as the anion of diethyl malonate, readily isomerise to ring opened products. Ligand exchange reactions and polymerisation compete with the nucleophilic addition reactions of neutral nucleophiles such as enol ethers and indole.     

Oxidative cleavage of α, β-unsaturated compounds by pentachlorohydroxoplatinate(IV) in alkaline medium

The kinetics of oxidation of α,β-unsaturated compounds by platinum(IV) in the presence of alkali {[OH⁻]= (1–9) × 10⁻³ mol dm⁻³} have been investigated over the 303–318 K temperature range . The rate of the reaction is dependent on the first power of the concentrations of substrates, oxidant, and alkali. The rate constant increases with an increase in ionic strength and also with increasing dielectric constant of the medium. The oxidation rates follow the order: –CN > –CONH₂ > –COO⁻. The values of the third order rate constant (k₃) for the oxidation of acrylonitrile, acrylamide and acrylate are 1.24, 0.826 and 0.628 mol⁻² dm⁶ s⁻¹ respectively, at 303 K. The oxidations of the substrates by PtCl₅(OH)²⁻ take place by an inner-sphere mechanism. Platinum(IV) is reduced to platinum(II) by the substrates in a one-step two-electron transfer process to give reaction products. The major reaction product, HCHO, is identified from the reaction mixture using i.r. spectrometry, n.m.r. and C, H, N analysis. A tentative reaction mechanism, leading to the formation of products, has been suggested. The activation parameters of the reaction have been evaluated.     

Isolation of Cyclic(Alkyl)(Amino) Carbene–Bismuthinidene Mediated by a Beryllium(0) Complex

The long-sought carbene–bismuthinidene, (CAAC)Bi(Ph), has been synthesized. Notably, this represents both the first example of a carbene-stabilized subvalent bismuth complex and the extension of the carbene-pnictinidene concept to a non-toxic metallic element (Bi). The bonding has been investigated by single-crystal X-ray diffraction studies and DFT calculations. This report also highlights the hitherto unknown reducing and ligand transfer capability of a beryllium(0) complex.     

Oxidative Deprotection of Cyclic Acetals and Trimethylsilyl Ethers by γγ-Picolinium Chlorochromate Under Nonaqueous Conditions

Deprotection of cyclic acetals and oxidative desilylation of trimethylsilyl ethers into the corresponding carbonyl compounds with -picolinium chlorochromate (-PCC) under nonaqueous conditions at room temperature is described. Oxidation of aldehydes to carboxylic acids was not observed in any case.     

Oxidative bisdecarboxylation of α-alkoxymalonic acids with cerium(IV)

Ceric ammonium nitrate is an excellent reagent for preparing carboxylic esters from α-alkoxymalonic acids by oxidative bisdecarboxylation.     

Electrochemical-Induced Ring Transformation of Cyclic α-(ortho-Iodophenyl)-β-oxoesters

Cyclic α-(ortho-iodophenyl)-β-oxoesters were converted in a ring-expanding transformation to furnish benzannulated cycloalkanone carboxylic esters. The reaction sequence started by electrochemical reduction of the iodoarene moiety. In a mechanistic rationale, the resulting carbanionic species was adding to the carbonyl group under formation of a strained, tricyclic benzocyclobutene intermediate, which underwent carbon–carbon bond cleavage and rearrangement of the carbon skeleton by retro-aldol reaction. The scope of the reaction sequence was investigated by converting cyclic oxoesters with different ring sizes yielding benzocycloheptanone, -nonanone and -decanone derivatives in moderate to good yields. Furthermore, acyclic starting materials and cyclic compounds carrying additional substituents on the iodophenyl ring were submitted to this reaction sequence. The starting materials for this transformation are straightforwardly obtained by conversion of β-oxoesters with phenyliodobis(trifluoroacetate).     

Synthesis of 2-Benzylthio-5-phenyl-3,4-disubstituted Thiophenes by Intramolecular Condensation of α-Oxo Ketene Dibenzyl~thioacetals

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ａｓａｋｉｎｄｏｆｖｅｒｓａｔｉｌｅｉｎｔｅｒｍｅｄｉａｔｅｓ ,α ｏｘｏｋｅｔｅｎｅｄｉｔｈｉｏａｃｅｔａｌｓ 1(Ｆｉｇ .1)ａｒｅｉｍｐｏｒｔａｎｔｉｎｏｒｇａｎｉｃｓｙｎｔｈｅ ｓｉｓ1ａｎｄｍｏｓｔｗｏｒｋｓａｒｅｆｏｃｕｓｅｄｏｎｔｈｅα ｏｘｏｋｅｔｅｎｅｄｉｍｅｔｈｙｌｔｈｉｏａｃｅｔａｌｓ .2 Ｉｎｏｕｒｓｔｕｄｉｅｓ ,ｉｔｉｓｆｏｕｎｄｔｈａｔｓｏｍｅｒｅａｃｔｉｏｎｓｕｐｏｎｔｈｅｓｅｋｉｎｄｏｆｉｎｔｅｒｍｅｄｉａｔｅｓａｒｅｍｏｄｕｌａｔｅｄｂｙｔｈｅ…