10.1016/j.tetlet.2007.11.050
The research focuses on the construction of the 3-prenyl-4-oxa-tricyclo[4.3.1.03,7]dec-8-en-2-one core, which is a key structural component found in caged xanthonoid natural products derived from Garcinia plants. The purpose of the study was to develop a two-step protocol utilizing tandem Wessely oxidation and intramolecular Diels–Alder reaction to access this core structure efficiently. The researchers successfully demonstrated the generality of this method through various examples, showing that the prenyl group could be installed in the required position. They also showed that these tricyclic scaffolds could be further transformed into substituted c-lactones through a photochemical 1,3-acyl shift and decarbonylation. Key chemicals used in the process include lead tetraacetate (LTA), acrylic acid, and various prenylated and oxygenated aromatic precursors. The study concluded that this two-step sequence is a versatile method for accessing the caged tricyclic system present in Garcinia xanthonoids and that the synthesized 4-oxa-tricyclo[4.3.1.03,7]dec-8-en-2-ones are valuable precursors for synthetically useful c-lactones.
10.1021/jo00060a040
The research focuses on the cleavage of unsaturated α-ketols to o-oxo-α,β-unsaturated acids, with the aim of developing an enantioselective synthesis of cyclic systems bearing contiguous quaternary centers, particularly those with gem-dimethyl groups. The study concludes that sodium periodate is the most effective reagent for this cleavage, outperforming other common oxidizing agents like sodium bismuthate, manganese dioxide, and lead tetraacetate, in terms of yield and efficiency. The combination of this cleavage reaction with a rhodium(I)-mediated decarbonylation of o-oxo-α,β-unsaturated esters derived from polycyclic systems was found to be a successful approach for the synthesis of the desired cyclic systems. Key chemicals used in the process include sodium periodate, sodium bismuthate, manganese dioxide, lead tetraacetate, and various α-ketols, among others, with the research providing detailed procedures and spectral data for the synthesized compounds.
10.1039/c39880000721
This research aims to develop a synthetic route for Aflatoxin B2, a highly toxic and carcinogenic metabolite produced by various Aspergillus species. The study focuses on synthesizing a ring A differentiated tetrahydrofurobenzofuran intermediate, which can be converted into Aflatoxin B2. Key chemicals used in the research include 3,5-dimethoxy phenol, ortho-iodophenol, lead tetra-acetate (LTA), di-isobutylaluminum hydride (DIBAL-H), and t-butyl mercaptide. The researchers successfully synthesized the intermediate compound through a series of reactions, including iodination, reduction, and cyclization, achieving an overall yield of approximately 4%. The study concludes that the synthesized intermediate can be further converted into Aflatoxin B2, demonstrating a feasible synthetic pathway. The research also highlights the challenges in differentiating the oxygen substituents on ring A and presents a method to selectively demethylate the intermediate using t-butyl mercaptide, achieving improved selectivity and yield. This work represents a significant advancement in the synthesis of aflatoxins and lays the foundation for further studies on their structure and toxicity.
10.1246/bcsj.66.3790
The study investigates the chlorodecarboxylation of 3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoic acid rotamers (ap-1 and sc-1) using lead(IV) acetate in benzene, with lithium chloride or benzyltriethylammonium chloride as chloride sources. The ap-isomer produces a chloride (ap-2) and a cyclized compound (3) through radical addition to a nearby benzene ring, while the sc-isomer forms a benzylic chloride (4) via hydrogen transfer from the benzylic position to the radical site in the 9-substituent, along with an acetonyl ester (5) and small amounts of a 1-acetoxymethyl compound (6) and an olefin (7). The study explores the effects of varying chloride source concentrations on product distributions and proposes mechanisms for the formation of these compounds based on the stability of the benzylic radical and participation of a methyl group.
10.1016/j.tet.2007.10.030
The research focuses on the synthesis and biological evaluation of isoflavone analogues derived from Dalbergia oliveri, a plant used in traditional Thai medicine for treating chronic ulcers. The purpose of the study was to investigate the potential of these compounds as mitosis inhibitor agents, specifically their cytotoxic effects against leukemia cell lines, their ability to inhibit microtubule assembly, and their antimicrobial activity. The researchers synthesized mucronulatol 1, violanone 2, and isoflavone 3 using an aryllead-mediated coupling reaction, which involved organolead reagents. The conclusions drawn from the study were that mucronulatol 1 exhibited significant cytotoxicity against the HBL100 leukemia cell line with an IC50 value of 5.7 mM, while all compounds modestly inhibited microtubule assembly, independent of their cytotoxic abilities. However, none of the compounds showed antibacterial activity, but were potent inhibitors of Fusarium oxysporum, a phytopathogenic fungal growth. The chemicals used in the synthesis process included 3-phenylthio-chroman-4-one, mucronulatol, violanone, and various reagents such as lead tetraacetate, tin compounds, and palladium on charcoal, among others.
10.1016/S0040-4039(00)96497-9
The research explores a synthetic route to aromatic o-diketones through the oxidation of N-aroylhydrazones of o-hydroxyaryl ketones using lead(IV) acetate (LTA). The purpose of the study was to investigate the potential of this oxidation reaction as a method for synthesizing o-diketones, which are valuable intermediates in the synthesis of various heterocyclic compounds. The researchers found that the reaction was efficient, yielding high-quality o-diketones with good yields. Key chemicals used in the study include N-aroylhydrazones of o-hydroxyaryl ketones as starting materials and lead(IV) acetate as the oxidizing agent. The study concluded that this method is superior to previous methods due to its simplicity, accessibility of starting materials, and high yields, making it a synthetically useful route for the preparation of o-diketones.
10.1016/S0040-4020(01)88040-6
The study presents a novel method for introducing electrophilic glycine equivalents into peptides by converting serine and threonine residues into a-acetoxyglycine derivatives using lead tetraacetate. The a-acetoxyglycine derivatives can then be reacted with various nucleophiles such as thiols, dithiols, and carbohydrates to modify peptide chains. The study also explores the conversion of these derivatives into more reactive chlorides and their subsequent reactions with amino acid esters and enamines, yielding peptides with modified amino acids and demonstrating high stereoselectivity. The method allows for the synthesis of peptides with unique polarities and structures, such as macrocycles and pseudopeptides, and is applicable even in the presence of oxidation-sensitive amino acids, with only histidine and tyrosine requiring side-chain protection.