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Covering: January 2012 to January 2018 Sesterterpenoids are a small family of terpenes that often possess intriguing biological profiles and complicated chemical structures. Their total syntheses are usually remarkably challenging, requiring methodological and strategic innovation. In this review, we summarize and discuss the total syntheses of sesterterpenoids published during the coverage period, and the key chemical transformations are highlighted.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Salts of various oniums such as ammonium, phosphonium, tellurium, arsonium, bismuthenium have been used as phase transfer catalyst in many oxidation reactions. These ions are also in use as carriers of anionic oxidants such as permanganate, chromate, dichromate, etc. Among these oniums, alkylammonium ions have been extensively studied. Alkylammonium ions are charged molecules, susceptible for acquiring hydrophobic characteristics through carboneous groups present in the molecule. Variation of these groups can tune the hydrophobicity of the oniums; thereby these molecules can acquire amphipathic characteristics. In different solutions, these ions aggregate to form different organized assemblies providing different localization sites for the oxidants. These oxidants exist as tight ion pairs with the oniums and follow different reaction mechanism during the oxidation reactions of various irganic substrates. The X-ray crystal strudies as well as reaction kinetics support the existence of tight ion pairs in both solid state and in solutions. The variation of substituent in the substrate, and the polarity of the solvent are found to have significant effect on the oxidation kinetics and reaction mechanism. Herein, we focus the review on the alkyl ammonium ions as carriers of oxidants and described the kinetics and reaction mechanism of the oxidation processes.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A compound of formula (I): (I) wherein Y is, Z is OR10, NR11R11 SR11, S(0)R11 S02R11, R10 is H, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, CO?R11, or a protecting group, and R11 is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, or alkoxyl; a process for making a compound of formula (I); and a process for making a prostaglandin or a prostaglandin analogue using a compound of formula (I). wherein Y is

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis and C-H bond functionalization is well foreseeable, and the joint force along this line has been demonstrated to be a powerful approach in making inert C-H bond functionalization more viable, predictable, and selective. In this review, we provide a comprehensive summary of organocatalysis in inert C-H bond functionalization over the past two decades. The review is arranged by types of inert C-H bonds including alkane C-H, arene C-H, and vinyl C-H as well as those activated benzylic C-H, allylic C-H, and C-H bonds alpha to the heteroatom such as nitrogen and oxygen. In each section, the discussion is classified by the explicit organocatalytic mode involved.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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In this full article, we report our efforts towards the total synthesis of aconitine (1), a representative C19-diterpenoid alkaloid that possesses perhaps one of the most architecturally intricate ring systems in nature. From (R)-(-)-carvone-derived 20, we first prepared chiral 2-methylenecyclohexane-1,3,5-triol derivative 19. A substrate-controlled intramolecular [3 + 2] cycloaddition of an in situ-generated nitrone intermediate 25 derived from 19 provides fully decorated A-ring building block 17. The first reported synthesis of fully functionalized aconitine AE fragment 16 is achieved from 17 by C11 hydroxylation, E-ring cyclization, and C5 one-carbon extension. Alkynylation of AE fragment 16 with CD fragment 15 gives radical cyclization precursors 14b and 14c. Efforts to achieve the challenging radical cyclization cascade of 14b and 14c under various conditions failed to produce the desired pentacyclic intermediate 12a in the route to aconitine (1).

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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This review of simple indolizidine and quinolizidine alkaloids (i.e., those in which the parent bicyclic systems are in general not embedded in polycyclic arrays) is an update of the previous coverage in Volume 55 of this series (2001). The present survey covers the literature from mid-1999 to the end of 2013; and in addition to aspects of the isolation, characterization, and biological activity of the alkaloids, much emphasis is placed on their total synthesis. A brief introduction to the topic is followed by an overview of relevant alkaloids from fungal and microbial sources, among them slaframine, cyclizidine, Steptomyces metabolites, and the pantocins. The important iminosugar alkaloids lentiginosine, steviamine, swainsonine, castanospermine, and related hydroxyindolizidines are dealt with in the subsequent section. The fourth and fifth sections cover metabolites from terrestrial plants. Pertinent plant alkaloids bearing alkyl, functionalized alkyl or alkenyl substituents include dendroprimine, anibamine, simple alkaloids belonging to the genera Prosopis, Elaeocarpus, Lycopodium, and Poranthera, and bicyclic alkaloids of the lupin family. Plant alkaloids bearing aryl or heteroaryl substituents include ipalbidine and analogs, secophenanthroindolizidine and secophenanthroquinolizidine alkaloids (among them septicine, julandine, and analogs), ficuseptine, lasubines, and other simple quinolizidines of the Lythraceae, the simple furyl-substituted Nuphar alkaloids, and a mixed quinolizidine-quinazoline alkaloid. The penultimate section of the review deals with the sizable group of simple indolizidine and quinolizidine alkaloids isolated from, or detected in, ants, mites, and terrestrial amphibians, and includes an overview of the “dietary hypothesis” for the origin of the amphibian metabolites. The final section surveys relevant alkaloids from marine sources, and includes clathryimines and analogs, stellettamides, the clavepictines and pictamine, and bis(quinolizidine) alkaloids.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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This account describes the convergent synthesis of (-)-okilactomycin. The first-generation approach focused on the assembly of two complex fragments through a Prins reaction of a dioxinone and alpha-hydroxy aldehyde. While this route was not ultimately successful, a related Maitland-Japp process employing a beta-keto ester in place of the dioxinone fragment provided the necessary union of functionalized intermediate, thereby establishing the full carbon framework of the natural product. The synthesis also employed a highly diastereoselective Lewis acid-promoted Diels-Alder reaction and an olefin ring-closing metathesis to close the strained 11-membered macrocycle of the natural product.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Leishmaniasis is a public health problem in tropical and subtropical areas of the world, including Venezuela. The incidence of treatment failure and the number of cases with Leishmania-HIV co-infection underscore the importance of developing alternative, economical and effective therapies against this disease. The work presented here analyzed whether terpenoids derived from betulin are active against New World Leishmania parasites. Initially we determined the concentration that inhibits the growth of these parasites by 50% or IC50, and subsequently evaluated the chemotactic effect of four compounds with leishmanicidal activity in the sub-micromolar and micromolar range. That is, we measured the migratory capacity of Leishmania (V.) braziliensis in the presence of increasing concentrations of compounds. Finally, we evaluated their cytotoxicity against the host cell and their effect on the infectivity of L. (V.) braziliensis. The results suggest that (1) compounds 14, 17, 18, 25 and 27 are active at concentrations lower than 10 muM; (2) compound 26 inhibits parasite growth with an IC50 lower than 1 muM; (3) compounds 18, 26 and 27 inhibit parasite migration at pico- to nanomolar concentrations, suggesting that they impair host-parasite interaction. None of the tested compounds was cytotoxic against J774.A1 macrophages thus indicating their potential as starting points to develop compounds that might affect parasite-host cell interaction, as well as being leishmanicidal.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The present invention is directed to compounds, tautomers and pharmaceutically acceptable salts of the compounds which are disclosed, wherein the compounds have the structure of Formula I, and the variables R1 and R2 are as defined in the specification. Corresponding pharmaceutical compositions, methods of treatment, methods of synthesis, and intermediates are also disclosed.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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An asymmetric synthesis of the fugu fish poison, (-)-tetrodotoxin, is described. The route to this extraordinary target employs a number of unique transformations, foremost of which are two stereospecific C-H bond functionalization reactions. Accordingly, Rh-catalyzed carbene and nitrene C-H insertions facilitate rapid entry to the cyclohexane core of the natural product and make possible the late-stage installation of the tetrasubstituted carbinolamine center. Copyright

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI