Solvent effects on catalytic activity of manganese porphyrins with cationic,anionic and uncharged meso substituents: Indirect evidence on the nature of active oxidant species

Oxidation of cyclohexene and styrene with sodium periodate and tetra‐n‐butylammonium periodate (TBAP) catalyzed by MnT(3‐MePy)P(OAc), MnT(4‐SO₃)PP(OAc) and MnTPP(OAc) has been studied in water, methanol, acetonitrile and dichloromethane as solvents. The results show significant dependence of the product distribution on the type of solvent and the electronic nature of the aryl substituents introduced at the porphyrin periphery. While the oxidation of cyclohexene and styrene in the presence of MnT(3‐MePy)P(OAc) and MnTPP(OAc) in water (also in methanol) gave the corresponding epoxides as nearly the sole product, performing the reactions in the presence of MnT(4‐SO₃)PP(OAc) yielded the products of allylic oxidation, cyclohexene‐2‐ol and cyclohexene‐2‐one and acetophenone as the major products. In the case of styrene, performing the reaction in the presence of MnT(4‐SO₃)PP(OAc), MnT(3‐MePy)P(OAc) and MnTPP(OAc) in acetonitrile gave a mixture of styrene oxide and acetophenone as the products. Under the same conditions, the oxidation of cyclohexene afforded cyclohexene oxide as approximately the exclusive product. Furthermore, the oxidation of olefins in dichloromethane gave the corresponding epoxide as the exclusive products. The product distributions observed in the protic and aprotic solvents were used to provide indirect evidence on the relative contribution and reactivity of high valent manganese oxo and periodato Mn(III) porphyrin species to the oxidation reactions.     

Three-Component,One-Pot Synthesis of New Functionalized Pyrrolines

The addition of acetylenic esters to diethyl acetamidomalonate in the presence of tert-butyl isocyanide leads to highly functionalized 1-pyrrolines and 2-pyrroline.     

Reactivity of Various α-Halo Ketones in One-Pot Synthesis of γ-Iminolactones

The highly reactive 1:1 intermediate generated in the reaction of tert-butyl isocyanide and dialkyl acetylenedicarboxylate is trapped by α-halo ketones to produce halogenated iminolactones as the sole product in good yields.     

A simple and clean method for multicomponent synthesis of spiro [indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives using SBA-Pr-SO3H as catalyst under solvent-free conditions

Sulfonic acid functionalized SBA-15 (SBA-Pr-SO₃H) as a new nanoporous solid acid catalyst was applied in the green one-pot synthesis of spiro[indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives via three-component reaction of isatins, malononitrile or cyanoacetic esters and barbituric acids under solvent-free conditions. SBA-Pr-SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm, which could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused several times without any loss of activity. The advantages of this methodology are high product yields, being environmentally benign, short reaction times, and easy handling.     

Synthesis and antibacterial activity of ethyl 2-amino-6-methyl-5-oxo- 4-aryl-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylate

The three-component reaction of 4-hydroxy-1-methyl-2(1H)-quinolinone, aromatic aldehydes and ethyl cyanoacetate was carried out in the presence of a catalytic amount of 4-dimethyl aminopyridine(DMAP) in aqueous ethanol. The reactions result in the formation of pyranoquinoline derivatives in excellent yields. Antibacterial activity has been evaluated against Gram positive and Gram negative bacteria for some of the synthesized compounds. The results indicated that these compounds are moderately effective against bacterial growth and their effectiveness is highest against Pseudomonas aeruginosa.     

Characterization and High Level Expression of Acidic Endoglucanase in Pichia pastoris

Bioconversion of cellulosic material into glucose needs cellulase enzymes. One of the most important organisms that produces cellulases is Trichoderma reesei, whose cellulose enzymes are probably the most widely used in the industry. However, these enzymes are not stable enough at high pH and temperatures. The optimized synthetic endoglucanase II gene with Pichia pastoris codon preferences was secretary expressed in P. pastoris. Recombinant enzyme characterization showed maximum activity at pH 4.8 and temperature 75 °C, and it demonstrated increasing thermal stability in high temperature. The enzyme maintained its activity in a wide pH range from 3.5 to 6.5. The optimization of fermentation medium was carried out in shaking flasks. Recombinant protein expression at optimum conditions (pH 7, temperature 25 °C, and 1 % methanol induction) for 72 h demonstrated 2,358.8 U/ml endoglucanase activity units. To our knowledge, this is the highest acidic thermophilic endoglucanase activity that is reported in crude intracellular medium in P. pastoris. We conclude that P. pastoris is an appropriate host for high-level expression of optimized endoglucanase gene with improved thermal stability.     

Diastereoselective synthesis of pyrrolo[1, 2-c]imidazoles using chiral thiohydantoins,malononitrile, and aldehydes and evaluation of their antioxidant and antibacterial activities

Diastereoselective synthesis of pyrrolo[1,2-c]imidazoles is reported from three-component reaction of chiral thiohydantoins, aldehydes, and malononitrile in the presence of NEt₃. The antioxidant properties of the obtained products were evaluated by 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay. Among the products, compound 4l possessing NH₂ and NH groups and bromine atom at 4-position of the aromatic ring displayed the highest antioxidant activity (90%). Also, their antibacterial activities were explored against gram-positive and gram-negative bacteria using disc diffusion method. Among the synthesized compounds, 4a with chlorine atom at para position of the aromatic ring, and methyl group (the smallest alkyl group) at 7-position, displayed the best antibacterial activity against the tested gram-positive bacteria.     

One-pot synthesis of new hydantoin (thiohydantoin) derivatives and evaluation of their antibacterial and antioxidant activities

One-pot four-component reactions of phenacyl bromides, parabanic or thioparabanic acids, thiophenols, and triphenylphosphine in the presence of triethylamine afforded new derivatives of hydantoin or thiohydantoin in good to high yields (65%-90%). Their antibacterial activities were evaluated against two Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Among the synthesized compounds, the obtained products from 2-hydroxythiophenol exhibited higher antibacterial activity than those obtained from 2-aminothiophenol. Compound 9l including N,N′^′-diphenyl thiohydantoin moiety showed the highest antibacterial activity (26.0 ± 01.4) against B subtilis, in comparison with other synthesized samples. The antioxidant activities of the synthesized hydantoins and thiohydantoins were investigated by DPPH radical-scavenging based on Blois method. The results showed that all the compounds have high DPPH inhibition potency (77.4%-83.9%) that it could be due to existence of heteroatoms with lone pair electrons and exchangeable protons on their NH₂ and OH groups.