Preparation of allylic ketones via acylation of allylic mercurials ; and, Palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles

The first part of this thesis discusses an unprecedented acylation of allylic mercurials by acyl chlorides promoted by aluminum chloride. A variety of allylic mercurials and acyl chlorides, including aliphatic, aromatic, and [alpha],[beta]-unsaturated acyl chlorides, can be employed successfully in this reaction. This reaction provides a convenient route to allylic ketones. A modified literature procedure to prepare allylic mercuric iodides from the corresponding allylic halides and metallic mercury is also presented in this part;The second part of this thesis discusses the palladium-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles, which generates more than one carbon-carbon bond or carbon-heteroatom bond at a time via palladium migration chemistry. Considerable functionality can be accommodated in this reaction and the palladium can migrate along a carbon chain as far as ten carbon atoms;The second part of this thesis is divided into three sections. The first section deals with the palladium-catalyzed coupling of aryl iodides and nonconjugated dienes using carbon nucleophiles. The reaction results in a high degree of regioselectivity and stereoselectivity. Applications of nitrogen and oxygen nucleophiles in this unique coupling reaction are reported in the second section. A variety of amines and the azide anion have been used as representative nitrogen nucleophiles and only one regio- and stereoisomer is isolated in good yields. When oxygen nucleophiles, such as acetate anion and phenoxide anion, are used in the coupling process, a mixture of regio- and stereoisomers is obtained. The focus of the third section is the application of the three-component coupling methodology to the synthesis of analogues of some naturally occurring pyridine alkaloids. The palladium-catalyzed coupling-migration approach is the key step and the total synthesis is accomplished in only two steps

Membrane expression and significance of TRAIL death receptors DR4 and DR5 in Pancreatic cancer

Introduction: Tumor necrosis factor related-apoptosis-inducing ligand (TRAIL) is a powerful and selective activator of apoptosis in many cancer cells. We aim to investigate the expression and significance of TRAIL death receptor DR4 and DR5 in pancreatic cancer (PC) tissues. Method: Twenty-eight histologically verified samples of PC tissue were collected between 2018 and 2019. TRAIL death receptor expression profiles were determined by immunohistochemistry. Result: Death receptor DR4 and DR5 were expressed in the PC tissue and the adjacent non-cancerous pancreatic tissues, the expression of DR4 and DR5 in the PC tissue was significantly higher than that of the adjacent non-cancerous pancreatic tissues (p<0.05). Additionally, in both the tissue group, the expression of DR4 was significantly stronger than the DR5 (p<0.05). To assess the relationship between DR4 and DR5 expression, differentiation, and tumor staging of PC, the result reveals that the expression of DR4 and DR5 was significantly higher in stage I tumors than the stage II, III, IV tumors (p<0.05). In contrast, the expression of DR4 and DR5 was decreased with a decrease in the degree of differentiation of tumors. However, the difference was not statistically significant. Conclusion: The membrane expression of TRAIL death receptor DR4 and DR5 is greater in PC than in the adjacent non-cancerous pancreatic tissues. Furthermore, increased membrane expression of TRAIL death receptor DR4 and DR5 in stage I PC and well-differentiated PC may predict the prognosis and feasibility of using TRAIL gene therapy as a treatment option for early PC.&nbsp