N-Heterocyclic carbene-catalyzed formation of β-anionic intermediates from enones has been employed in the enantioselective synthesis 2-aryl propionates. The reaction was achievable using a homochiral 4-MeOC6H4 morpholinone catalyst allowing first example catalysis by umpolung α,β-unsaturated ketones. is high yielding, and shows robustness with reasonable generality. A mechanism proposed which enantiodetermining protonation achieved either hexafluoroisopropanol or formed naphthol product.

Flavin-dependent 'ene'-reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in presence a photoredox catalyst. Experimental evidence suggests reaction proceeds via radical mechanism where pyridine is reduced corresponding neutral benzylic...

The catalytic umpolung of imines remains an underdeveloped approach to reaction discovery. Herein we report enantioselective aza-Stetter that proceeds via imine using N-heterocyclic carbene catalysis. with high levels enantioselectivity (all ≥96:4 er) and good generality (21 examples). Mechanistic studies are reported consistent turnover-limiting addition the NHC imine.

Non-natural photoenzymatic reactions reported to date have depended on the excitation of electron donor-acceptor complexes formed between substrates and cofactors within protein active sites facilitate transfer. While this mechanism has unlocked new reactivity, it limits types that can be involved in area catalysis. Here we demonstrate direct flavin hydroquinone "ene"-reductase enables participate reactions. We found by using photoexcitation these enzymes gain ability reduce acrylamides...

ConspectusConjugate acceptors are one of the most common electrophilic functional groups in organic synthesis. While useful a diverse range transformations, their applications largely dominated by reactions from which name is derived (i.e., as an acceptor nucleophiles conjugate position). In 2014, we commenced studies focused on ability to undergo polarity inversion through addition Lewis base catalysts. The first step this process provides enolate, well-developed Rauhut-Currier (RC) and...

A full account of our oxidative radical cyclization approach to the synthesis garcibracteatone and doitunggarcinone is presented. This includes first enantioselective garcibracteatone, which allowed absolute configuration natural compound be determined. The also described, confirms reassignment relative this molecule. Novel syntheses monoterpene fragments used construct target molecules are reported.

Herein we report the cycloisomerization of electron-poor 1,5-dienes via β-azolium ylide to give enantioenriched cyclopentenes. The reaction is mediated by a chiral N-heterocyclic carbene (NHC) catalyst, exploits readily available substrates, has good generality (17 examples), and displays excellent enantioselectivity (mostly >94:6). Studies demonstrating viability related dynamic kinetic resolution are reported, as those with alternate tethers derivatizations.

Abstract N‐Heterocyclic carbene‐catalyzed formation of β‐anionic intermediates from enones has been employed in the enantioselective synthesis 2‐aryl propionates. The reaction was achievable using a homochiral 4‐MeOC 6 H 4 morpholinone catalyst allowing first example catalysis by umpolung α,β‐unsaturated ketones. is high yielding, and shows robustness with reasonable generality. A mechanism proposed which enantiodetermining protonation achieved either hexafluoroisopropanol or formed naphthol product.

Polarity inversion is the hallmark of N-heterocyclic carbene (NHC) organocatalysis, with generation and reaction acyl anion equivalents known for more than 70 years. In contrast, polarity through 1,4-addition NHCs to conjugate acceptors was first applied in a catalytic 2006. This sub-field NHC-organocatalysis has developed steadily over subsequent years, enabling novel coupling reactions, enantioselective cycloisomerizations, polymerizations, other reactions. this review, emerging area...

The effects of peroxisome proliferator-activated receptor (PPAR)β/δ ophthalmic solution were investigated in a rat corneal alkali burn model. After injury, GW501516 (PPARβ/δ agonist) or vehicle was topically instilled onto the rat’s cornea twice day until 7. Pathological findings evaluated, and real-time reverse transcription polymerase chain reaction performed. strongly suppressed infiltration neutrophils pan-macrophages, reduced mRNA expression interleukin-6, interleukin-1β, tumor necrosis...

FROUNT is an intracellular protein that promotes pseudopodia formation by binding to the chemokine receptors CCR2 and CCR5 on macrophages. Recently, disulfiram (DSF), a drug treatment for alcoholism, was found have inhibitory activity. In this study, we investigated effect of DSF eye drops in rat corneal alkali burn model. After burn, 0.5% (DSF group) vehicle (Vehicle were administered twice daily. Immunohistochemical observations real-time reverse transcription-polymerase chain reaction...

Iodobenzene-catalyzed 1,2-olefin functionalization via C-C and C-O bond formation has been achieved with electron rich aromatic groups vinylogous esters acting as independent nucleophiles. The reaction provides oxabicyclo[3.2.1]octanes [4.2.1]nonanes from commercially available 3-alkoxy cycohexen-2-ones in three steps.

Peroxisome proliferator-activated receptor alpha (PPARα) and gamma (PPARγ) agonists have anti-inflammatory anti-neovascularization effects, but few reports tested the combination of PPARα PPARγ agonists. In this study, we investigated therapeutic effects ophthalmic solutions PPARα, PPARγ, in a rat corneal alkali burn model. After injury, an solution 0.05% fenofibrate (PPARα group), 0.1% pioglitazone (PPARγ + (PPARα+γ or vehicle (vehicle group) was topically instilled onto rat’s cornea twice...

Lewis base catalysis by lone pair donation into anti-bonding π orbitals (n–π*) is a growing field with range of bases capable this type catalysis. In review, the Morita–Baylis–Hillman reaction, Steglich rearrangement, and annulation α,β-unsaturated acyl adducts are discussed, using N-heterocyclic carbene (NHC), isothiourea, bicyclic tertiary amine electron-rich pyridyl catalysts. many cases, each these popular catalysts viable for given degree utility defined catalyst's nucleophilicity...

Abstract The catalytic umpolung of imines remains an underdeveloped approach to reaction discovery. Herein we report enantioselective aza‐Stetter that proceeds via imine using N‐heterocyclic carbene catalysis. with high levels enantioselectivity (all ≥96:4 er) and good generality (21 examples). Mechanistic studies are reported consistent turnover‐limiting addition the NHC imine.

Dimethyl carbamoyl tetrahydrocarbazoles undergo directed oxidation using standard conditions to exclusively provide products from C(sp3)–H oxidation. This result is in contrast recent studies on the C–H olefination of hydrocarbazoles, which selective aromatic functionalisation.

Glutathione transferase omega-1 (GSTO1-1) is an enzyme whose function supports the activation of interleukin (IL)-1β and IL-18 that are implicated in a variety inflammatory disease states for which small-molecule inhibitors sought. The potent reactivity active-site cysteine has resulted reported act by covalent labeling. In this study, structure–activity relationship (SAR) elaboration GSTO1-1 inhibitor C1-27 was undertaken. Compounds were evaluated inhibitory activity toward purified...

The theory of KM_{2}O-Langevin equations and its applications to data analysis ( I):Stationary 47 where d N are any fixed natural numbers.We call such a process X local weakly stationary time series.In subsection [2. 1] \S 2, we extract two kinds d-dimensional orthogonal series \nu_{+}=(\nu_{+}(n) ; 0\leq n\leq N) \nu_{-}=(1/-(-n) from the original X, by taking innovation approach ([13]).It is noted that either condition (2. 5) 6) holds for block Toeplitz matrices S_{n} composed R.Under...

Dextromethorphan was N-demethylated using the non-classical Polonovski reaction under continuous flow conditions, in two steps: initial N-oxidation with m-chloroperbenzoic acid followed by iron-catalysed N-demethylation of resulting N-oxide.

Abstract Flavin‐dependent ‘ene’‐reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in presence a photoredox catalyst. Experimental evidence suggests reaction proceeds via radical mechanism where pyridine is reduced corresponding neutral...