Carbon–carbon/carbon–heteroatom bond formation via oxidative transformations is a heavily explored topic at the frontier of chemistry. Potassium persulfate (K2S2O8) has emerged as cost-effective, suitable inorganic oxidant for wide array transformations, ranging from laboratory experiments to industrial processes. The current review provides comprehensive coverage aided with K2S2O8 in presence or absence transition-metal catalyst, critical assessment results, and underlying mechanisms....

A one-flask synthesis of meso-substituted dipyrromethanes has been refined. The procedure entails reaction an aldehyde in 100 equiv pyrrole as the solvent containing a mild Lewis acid (e.g., InCl3) at room temperature. Following removal and recovery excess pyrrole, dipyrromethane is obtained by crystallization. generates minimal waste does not require aqueous/organic extraction, chromatography, or distillation. scaled linearly to obtain >100 g 5-phenyldipyrromethane. utility various...

Abstract Lipase‐catalyzed organic reactions have widely been practiced in the past three decades. In addition to its wide acceptance conventional such as hydrolysis, transesterification, and enantiopure synthesis (kinetic resolution dynamic kinetic resolution) several reports on catalytic promiscuity of lipases also published. The concept promiscuity, where lipase catalyzes beyond natural function, has perceived a useful phenomenon which can enhance utility biocatalyst. Many Aldol...

A direct one-pot approach to the synthesis of carbazoles (mono-, di-, and trisubstituted) α-carbolines from readily available indoles or 7-azaindoles alkenes is described. Based on mechanistic studies, tandem reaction follows sequence: palladium-catalyzed regioselective C-3 alkenylation/palladium-catalyzed C-2 alkenylation/thermal electrocyclization.

Etomidate is a sedative hypnotic that often used in critically ill patients because it provides superior hemodynamic stability. However, also binds with high affinity to 11beta-hydroxylase, potently suppressing the synthesis of steroids by adrenal gland are necessary for survival. The authors report results studies define pharmacology (R)-ethyl 1-(1-phenylethyl)-1H-pyrrole-2-carboxylate (carboetomidate), pyrrole analog etomidate specifically designed not bind 11beta-hydroxylase.The potency...

The palladium-catalyzed intramolecular oxidative coupling described herein involves a double C(sp(2))-H bond functionalization in sulfonanilides, providing workable access to biaryl sultams annulated into six-membered ring that are otherwise difficult obtain by literature methods. other synthetic applications of this protocol including the synthesis containing seven-membered and analogous sultones also presented.

The installation of sulfonamide pharmacophores on heterobiaryls has successfully been executed by a previously unknown palladium-catalyzed intramolecular oxidative coupling in N-arylsulfonyl heterocycles followed novel ring opening heterobiaryl sultams with amine nucleophiles. protocol wide scope substrates warranting broad applications the synthesis containing an o-sulfonyl or carboxyl functional group.

A comprehensive package including new amide formation, their intramolecular reactions for the synthesis of diverse nitrogen heterocycles, and preparation a marketed drug is described.

Synthetic chlorins bearing diverse auxochromes at the 3- and 13-positions of macrocycle are valuable targets given their resemblance to chlorophylls a b, which bear 3-vinyl 13-keto groups. A de novo route has been exploited construct nine zinc substituents two benchmark lacking such substituents. The sterically uncongested (1) geminal dimethyl group in reduced pyrroline ring, (2) H, an acetyl, triisopropylsilylethynyl (TIPS-ethynyl), or vinyl 3-position, (3) TIPS-ethynyl 13-position, (4) H...

Abstract The optical absorption spectra and redox properties are presented for 24 synthetic zinc chlorins 18 free base analogs bearing a variety of 3,13 (β) 5,10,15 (meso) substituents. Results also given oxophorbine, which contain the keto‐bearing isocyclic ring present in natural photosynthetic pigments such as chlorophyll . Density functional theory calculations were carried out to probe effects types positions substituents on characteristics (energies, electron distributions) frontier...

A general synthetic route to prepare all four carboline regioisomers by photostimulated cyclization of anilinohalopyridines is described. The methodology affords various substituted carbolines in good excellent yields. In the case α-carbolines, SRN1 complements previously reported palladium-catalyzed approaches.

A one-pot synthesis of α-carbolines via a palladium-catalyzed aryl amination followed by intramolecular arylation is described. 2,3-Dichloro- and 2,3-dibromopyridines have been shown to react with readily available anilines obtain various substituted in moderate excellent yields.

A transition-metal-free, K2S2O8-mediated intramolecular oxidative nitrogenation/oxygenation of C(sp3)–H in N-aryl benzylic amines followed by oxidation at the center has been developed for synthesis benzamidine/benzoxazine heterocycles, providing an expedient access to quinazolin-4(3H)-ones, N-aryl-2-arylbenzimidazoles, and 4H-3,1-benzoxazin-4-ones. considerable amount work dealing with mechanistic study understand crucial cyclization step largely favors iminium ion as key intermediate.

The development of Minisci acylation on electron-rich pyrroles under silver-free neutral conditions has been reported featuring the regioselective monoacylation (NH)-free pyrroles. Unlike conventional conditions, avoidance any acid that could result in polymerization was key to success. umpolung reactivity nucleophilic acyl radical, generated situ from arylglyoxylic acid, help explain mechanism product formation with Alternatively, substitution radical electron-deficient pyrrole cation is proposed.

A diverse functionalization and synthesis of heterocycles using K 2 S O 8 as oxidant glucose persulfate activator in water at room temperature is reported.

Understanding the effects of substituents on spectra chlorins is essential for a wide variety applications. Recent developments in synthetic methodology have made possible systematic studies properties chlorin macrocycle as function diverse types and patterns substituents. In this paper, spectral, vibrational excited-state decay characteristics are examined set chlorins. The bear at 5,10,15 (meso) positions or 3,13 (beta) (plus 10-mesityl series compounds) include 24 zinc chlorins, 18 free...

We previously developed 2 etomidate analogs that retain etomidate's favorable hemodynamic properties but whose adrenocortical effects are reduced in duration or magnitude. Methoxycarbonyl (MOC)-etomidate is rapidly metabolized and ultrashort acting whereas (R)-ethyl 1-(1-phenylethyl)-1H-pyrrole-2-carboxylate (carboetomidate) does not potently inhibit 11β-hydroxylase. hypothesized MOC-etomidate's labile ester could be incorporated into carboetomidate to produce a new agent possesses...

Nitrogen-containing fused heterocycles comprise many compounds that demonstrate interesting biological activities. A new synthetic approach involving Mitsunobu alkylation of imidazoles, pyrroles, and indoles followed by palladium-catalyzed cyclization has been developed providing access to with a defined stereochemistry α nitrogen. While ethyl imidazole or indole carboxylates are good substrates for optically pure secondary benzylic alcohols, the corresponding pyrroles poor presumably due...

A novel tandem oxidative conversion of 10,11-dihydro-5H-dibenzo[b,e][1,4]diazepines to phenazines has been achieved under transition-metal-free, mild conditions using K2S2O8 or DDQ as the oxidizing agent. The transformation proceeds through removal a benzylic methylene group by C–C and C–N bond cleavage followed new aryl formation radical conditions.