Sulfonyl fluorides have found increasing applications as functional molecules in chemistry and biology. We herein report a copper-catalyzed atom-economical access to two categories of sulfonyl through radical relay strategy the presence an SO2 surrogate. The aliphatic C(sp3)–H bond N-fluoro-N-alkyl sulfonamides reacted via 1,5-hydrogen atom transfer (HAT) process, affording alkanesulfonyl with proximal amino group. On other hand, utilizing substrates containing proper C═C double resulted...

The complicated mechanism makes the regiodivergent rearrangement of ammonium ylide seem to be out reach. Herein, we reported a gramine well controlled by substituents. Density functional theory studies reveal that with more steric hindrance substituent 2-diazo-2-arylacetate goes through stepwise yield both kinetically and thermodynamically preferred [1,2]-rearrangement product. In contrast, less ethyl diazoacetate concerted generate [2,3]-rearrangement product, which is favored as result...

The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns Compound I, II, and protonated II with model substrates, address question which these compounds is most effective oxidant? All calculations, regardless substrate, implicated I superior oxidant three. However, were found to react free energies activation only few kcal mol-1...

Bioinspired manganese complexes have emerged as attractive catalysts for a number of selective oxidation reactions over the past several decades. In present study, we report enantioselective spirocyclic compounds with bearing tetradentate N4 ligands and aqueous H2O2 terminal oxidant under mild conditions; tetralone (1a) its derivatives electron-donating -withdrawing substituents are converted to their corresponding chiral β,β′-diketones high yields enantioselectivities. Spirocyclic indanones...

We report for the first time electron-transfer (ET) properties of mononuclear nonheme iron-oxo and -imido complexes with formal oxidation states five six, such as an iron(V)-imido TAML cation radical complex, which is formally iron(VI)-imido complex [FeV(NTs)(TAML+•)] (1; NTs = tosylimido), [FeV(NTs)(TAML)]− (2), iron(V)-oxo [FeV(O)(TAML)]− (3). The one-electron reduction potential (Ered vs SCE) 1 was determined to be 0.86 V, much more positive than that 2 (0.30 V), but Ered 3 most (1.04 V)....

Biomimetic iron and manganese complexes have emerged as important catalysts in chemo-, regio-, stereoselective oxidation reactions. In this study, we describe a remote hydroxylation of undirected C(sp3)–H bonds utilizing simple complex catalyst hydrogen peroxide (H2O2) terminal oxidant the presence bromoacetic acid (BrCH2CO2H) an additive. Crucial features catalytic system are excellent activity easily preparable catalyst, [Mn(R,R-BPMCN)]2+ (1), low loading, short reaction time, broad...

Axially chiral biaryls featuring a C–N axis are important functional molecules in diverse fields. The asymmetric Buchwald–Hartwig reaction represents powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due the steric and entropic effects reductive elimination of Pd(II) species with sterically congested aryl nitrogen groups. We now report two intermolecular coupling systems bulky NH lactams...

The highly efficient catalytic oxidation and oxidative kinetic resolution of secondary alcohols has been achieved using mononuclear Mn(<sc>ii</sc>) catalysts H₂O₂.

Mononuclear nonheme manganese complexes are highly efficient catalysts in the catalytic oxidation of hydrocarbons by hydrogen peroxide presence carboxylic acids. Although high-valent Mn(V)-oxo have been proposed as active oxidants that afford high regio-, stereo-, and enantioselectivities reactions, importance spin state (e.g., S = 0 or 1) species is an area requires further study. In present study, we theoretically demonstrated a mononuclear with 1 ground oxidant effects stereo-...

The nature of reactive intermediates and the mechanism cis-dihydroxylation arenes olefins by Rieske dioxygenases synthetic nonheme iron catalysts have been topic intense research over past several decades. In this study, we report that a spectroscopically well characterized mononuclear iron(III)-peroxo complex reacts with naphthalene derivatives, yielding iron(III) cycloadducts are isolated structurally spectroscopically. Kinetics product analysis reveal is nucleophile naphthalenes to yield...

The carbon-to-silicon switch in formation of bioactive sila-heterocycles with a silicon-stereogenic center has garnered significant interest drug discovery. However, metal-catalyzed synthesis such scaffolds is still its infancy. Herein, rhodium-catalyzed enantioselective formal [4+1] cyclization benzyl alcohols and benzaldimines been realized by difunctionalization secondary silane reagent, affording chiral-at-silicon cyclic silyl ethers sila-isoindolines, respectively. Mechanistic studies...

Metal-catalyzed synthesis of Si-stereogenic monohydrosilanes with remote unsaturated groups remains challenging due to the potential self-overfunctionalization. Herein, we report a CuH-catalyzed enantioselective hydrosilylation strained methylenecyclopropanes, affording various remote...

Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such related oxidation mechanism are still unsolved after decades experimental efforts. Density functional calculations were employed to explore structure-reactivity relationship iron(III)-iodosylbenzene complex, [FeIII(tpena-) (PhIO)]2+ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic...

Mononuclear nonheme iron(III)-hydroperoxo intermediates play key roles in biological oxidation reactions. In the present study, we report highly intriguing reactivity of a iron(III)–hydroperoxo complex, [(TMC)FeIII(OOH)]2+ (1), deformylation aldehydes, such as 2-phenylpropionaldehyde (2-PPA) and its derivatives; that is, reaction pathway aldehyde by 1 varies depending on conditions, temperature substrate. At above 248 K, occurs predominantly via nucleophilic addition (NA) pathway. However,...

We report the macrocyclic ring size–electronic structure–electrophilic reactivity correlation of mononuclear nonheme iron(III)-peroxo complexes bearing N-tetramethylated cyclam analogues (n-TMC), [FeIII(O2)(12-TMC)]+ (1), [FeIII(O2)(13-TMC)]+ (2), and [FeIII(O2)(14-TMC)]+ (3), as a model study Rieske oxygenases. The Fe(III)-peroxo show same δ pseudo-σ bonds between iron peroxo ligand. However, strength these interactions varies depending on size n-TMC ligands; overall Fe–O bond Fe–O2...

Dopamine receptors are important in systemic blood pressure regulation. D4 expressed the kidney and brain, but their role cardiovascular regulation is unknown. In pentobarbital-anesthetized mice, systolic diastolic pressures were elevated sixth-generation receptor-deficient (D4(-/-)) mice tenth-generation D4(-/-) compared with wild-type (D4(+/+)) littermates. The conscious measured via a chronic arterial (femoral) catheter or telemetry (carotid) also higher than Basal renal plasma renin...

Mn(III)-iodosylarene porphyrin adducts, [Mn(III)(ArIO)(Porp)]+, were synthesized by reacting electron-deficient Mn(III) complexes with iodosylarene (ArIO) at −60 °C and characterized using various spectroscopic methods. The [Mn(III)(ArIO)(Porp)]+ species then investigated in the epoxidation of olefins under stoichiometric conditions. In species, epoxide was formed as sole product high chemoselectivities stereoselectivities. For example, cyclohexene oxide exclusively trace amounts allylic...

Understanding the reaction mechanisms, particularly chiral induction mode, is critical for development of new asymmetric catalytic reactions. Rhodium(III)-catalyzed C–H activation en route to atroposelective [4 + 2] annulative coupling with α-diazo β-ketoesters has been realized, affording axially phenanthrenes in good excellent enantioselectivity. A combination experimental and computational studies revealed a nontraditional stereodivergent–convergent mode. The proceeded rhodafluorene...

A stereodivergent synthesis of β- and α-O-glycosides using 3-O-quinaldoyl glucals was developed by palladium catalysis at 60 110 °C respectively. Various alcohols, monosaccharides, amino acid were glycosylated to form α- products in good yields with high stereoselectivity. Mechanistic studies indicated no classic Pd–N (quinoline) coordination, but π–π stacking interactions promoted the anomeric stereodiversity. The practicality demonstrated glycosylating natural products/drugs synthesizing a...

Post-stroke inflammation is almost involved in the whole process of stroke pathogenesis, which serves as a prime target for developing new therapies. Despite known sex differences incidence and outcome stroke, few preclinical or clinical studies take into account bias treatment. Recent evidence suggests that poly (ADP-ribose) polymerase (PARP)-1 inhibitor exerts sex-specific neuroprotection ischemic stroke. This study was aimed to investigate effects delayed PARP-1 inhibition on post-stroke...

Acid effects on the chemical properties of metal–oxygen intermediates have attracted much attention recently, such as enhanced reactivity high-valent metal(IV)–oxo species by binding proton(s) or Lewis acidic metal ion(s) in redox reactions. Herein, we report for first time proton an iron(V)–oxo complex bearing a negatively charged tetraamido macrocyclic ligand (TAML) oxygen atom transfer (OAT) and electron-transfer (ET) First, synthesized characterized mononuclear nonheme Fe(V)–oxo TAML (1)...

The one-electron reduction product, ˙CCl₃, irreversibly inactivates P450 <italic>via</italic> covalently binding to the <italic>meso</italic>-carbon, whereas two successive reductions :CCl₂, reversibly inhibits by coordinating iron.

The rate constants of the C═C epoxidation and C-H hydroxylation (i.e., allylic bond activation) in oxidation cyclohexene by a high-valent iron(IV)-oxo porphyrin π-cation radical complex, [(TMP•+)FeIV(O)(Cl)] (1, TMP = meso-tetramesitylporphyrin dianion), were determined at various temperatures analyzing overall products obtained 1, leading us to conclude that reaction pathway changes from decreasing temperature. When was replaced deuterated (cyclohexene-d10), dominated irrespective...

Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization 1,6‐diynes with three distinct classes arenes, enabling highly broad range axially 1,3‐dienes that conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded excellent...

The incorporation of fluorine atoms into three-dimensional sp