Dimerization of 3-substituted 2-oxindoles
has been developed under
a mild electrochemical condition, avoiding toxic chemical oxidants
and metal by-products. This methodology forms a C(sp3)–C(sp3) bond at the pseudobenzylic position of two partners of 2-oxindoles
with a broad substrate scope. These dimeric structural motifs are
important building blocks for the total synthesis of pyrroloindoline
alkaloids. Furthermore, this work demonstrates in-depth mechanistic
insights employing electrochemistry, which suggests a stepwise one
proton transfer (PT) and two electron transfer (ET) processes. Most
significantly, reaction rate acceleration has been demonstrated by
exploiting the base-assisted proton-coupled electron transfer (PCET)
pathway. Hence, this work brings a new dimension in the field of electro-organic
synthesis with the help of nature’s favorite kinetic route,
i.e., PCET, to lower the kinetic barrier.
An efficient electrochemical strategy has been developed for the total synthesis of dimeric hexahydropyrrolo[2,3-b]indole alkaloids. In particular, oxidative dimerization of 3-alkyl 2-oxindoles was developed for this study. A detailed CV...
Dimerized 3-substituted 2-oxindoles are essential building
blocks
for the total synthesis of alkaloids. Herein, three different types
of 3-substituted-2-oxindoles were dimerized with a total of 41 examples
employing TEMPO as a redox mediator and TEMPO+ as an in
situ generated electrocatalyst using control potential electrolysis
at an applied potential of only 0.8 V versus a Ag/Ag+ nonaqueous
reference electrode. These reactions did not yield any product formation
in the absence of TEMPO, keeping other experimental conditions the
same. Two-electron- and one-electron-transfer pathways were operational
depending on the oxidation potentials of 2-oxindoles. 3-Carboxylate-2-oxindoles
having a lower oxidative energy barrier for a two-electron-transfer
pathway followed a hydride-transfer mechanism to generate a carbocation,
which thereafter reacted with the enol form of oxindole to produce
dimerized 2-oxindoles. On the other hand, 3-alkyl-2-oxindoles and
3-alkylcarboxylate-2-oxindoles had significantly higher oxidative
energy barrier compared to 3-carboxylate-2-oxindoles and followed
the one-electron-transfer pathway to generate a radical species for
dimerization. The two-electron transfer pathway was significantly
faster compared to the one-electron transfer pathway, evident from
reaction time (15 min vs 1 h 20 min or longer), which was due to a
faster second-order rate constant for the two-electron transfer pathway
(1.2 M–1 s–1) compared to the
one-electron transfer pathway (0.29 M–1 s–1). Furthermore, four aspects of transforming greener electro-organic
synthesis have been demonstrated. They are as follows: (a) electron-transfer
rate measurement as an alternative method for synthesis optimization
instead of lengthy product isolation, (b) prevention of electrode
passivation employing electrocatalysis routes, (c) recovery of the
electrolyte, and (d) mild reaction conditions employing control potential
electrolysis. Finally, an efficient electrochemical oxidation strategy
has been demonstrated for the total synthesis of a dimeric hexahydropyrrolo[2,3-b]indole alkaloids, (±)-chimonanthine (I) and (±)-folicanthine (II).
Objectives: This study aimed to determine the seroprevalence of brucellosis among pigs of commercial farms in Chitwan district of Nepal.
Methods: This cross sectional prospective study was conducted among 100 pigs of commercial farms located in western region of Chitwan district of Nepal. Blood sample was collected from each pig by the trained veterinarians and serum was extracted. Each serum sample was processed for Rose Bengal plate test (RBPT) and ELISA for the detection of Brucella spp. Data was analyzed using SPSS software version 21.0 and a p-value of less than 0.05 was considered as significant.
Results: Prevalence of brucellosis in pigs was found to be 15% (15/100) by RBPT and 10% (10/100) by ELISA. There was statistically insignificant difference (p=0.98) in gender wise prevalence of brucellosis among pigs. Younger pigs below one year of age were more susceptible to brucellosis than the older pigs. Landrace breed showed more positive test results compared to other breeds.
Conclusion: Pigs can be the potential source of transmission of brucellosis to humans. Considering the high economic loss on livestock sector and possible transmission to humans, awareness program and appropriate control strategies is warranted. Breed and age factors should be considered while adopting the control measures of brucellosis among pigs.
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