Functionalisation of saturated heterocycles via aerobic C-H activation to form C-C bonds

This project is focused on the transformation of heterocycles by exploiting their interaction with oxygen in air as a means to construct C–C bonds via radical addition. Chapter one introduces fundamental information about radical reactivity, C–H bond transformations and aerobic C–H activation work. Furthermore, the reactions of radical acceptors used in this thesis are introduced alongside current methods for functionalising heterocycles. Chapter two describes the research and development section of this work, where an optimised reaction is developed for the C–C bond formation of heterocycles via an aerobic oxidation pathway. Alkynyl hypervalent iodine and acetylenic triflone radical acceptors are shown to be compatible with differing success in the designed reaction conditions. Following this, exemplification of the alkynylation reaction is demonstrated by reaction scope studies for both the heterocycles and radical acceptors. The method was also shown to be compatible with vinyl triflones allowing access to vinyl heterocycles in one step. The use of the products formed was demonstrated by novel transformations to generate privileged scaffolds and fundamental building blocks of varying oxidation levels. Mechanistic studies are carried out to confirm both the aerobic and radical nature of the developed reaction conditions. Future directions are also highlighted as a result of the findings in this thesis, finally the last chapter contains the experimental results and characterisations of compounds mentioned within the thesis

Functionalisation of ethereal-based saturated heterocycles with concomitant aerobic C–H activation and C–C bond formation

With an ever-growing emphasis on sustainable synthesis, aerobic C–H activation (the use of oxygen in air to activate C–H bonds) represents a highly attractive conduit for the development of novel synthetic methodologies. Herein, we report the air mediated functionalisation of various saturated heterocycles and ethers via aerobically generated radical intermediates to form new C–C bonds using acetylenic and vinyl triflones as radical acceptors. This enables access to a variety of acetylenic and vinyl substituted saturated heterocycles that are rich in synthetic value. Mechanistic studies and control reactions support an aerobic radical-based C–H activation mechanism

Pancreatic Cystic Lesions: A Focused Review on Cyst Clinicopathological Features and Advanced Diagnostics

Macroscopic, endomicroscopic, and histologic findings and correlation are an integral part of the diagnostic evaluation of pancreatic cystic lesions (PCLs), as complementing morphologic features seen by different specialties are combined to contribute to a final diagnosis. However, malignancy risk stratification of PCLs with worrisome features can still be challenging even after endoscopic ultrasound guided-fine needle aspiration (EUS-FNA) with cytological evaluation. This review aims to summarize cyst clinicopathological features from the pathologists’ perspective, coupled with knowledge from advanced diagnostics–confocal laser endomicroscopy and cyst fluid molecular analysis, to demonstrate the state-of-art risk stratification of PCLs. This review includes illustrative photos of surgical specimens, endomicroscopic and histologic images, and a summary of cyst fluid molecular markers

Pancreatic Cystic Lesions: A Focused Review on Cyst Clinicopathological Features and Advanced Diagnostics

Macroscopic, endomicroscopic, and histologic findings and correlation are an integral part of the diagnostic evaluation of pancreatic cystic lesions (PCLs), as complementing morphologic features seen by different specialties are combined to contribute to a final diagnosis. However, malignancy risk stratification of PCLs with worrisome features can still be challenging even after endoscopic ultrasound guided-fine needle aspiration (EUS-FNA) with cytological evaluation. This review aims to summarize cyst clinicopathological features from the pathologists’ perspective, coupled with knowledge from advanced diagnostics–confocal laser endomicroscopy and cyst fluid molecular analysis, to demonstrate the state-of-art risk stratification of PCLs. This review includes illustrative photos of surgical specimens, endomicroscopic and histologic images, and a summary of cyst fluid molecular markers