A new approach towards a total synthesis of paeoniflorigenin is discussed. The approach involves the application of regio- and stereoselective [2+2] photocycloaddition for the preparation of a key intermediate, cyclobutanone 86, and model studies on diiodosamarium (Sm12) mediated pinacol coupling of a diketone. Intermolecular [2+2] photocycloaddition of a,13unsaturated lactam 33...
Coibamide A is a highly methylated cyclic depsipeptide isolated from Panamanian marine filamentous cyanobacteria as part of an International Cooperative Biodiversity Groups (ICBG) program based in Panama. This structurally unique agent exhibits potent cancer cell toxicity with an unprecedented selectivity profile in the National Cancer Institute (NCI) 60 cell line...
This dissertation describes the racemic and enantioselective synthesis cavicularin. Cavicularin is a macrocyclic bisbibenzyls family member natural product. It has been an attractive synthetic target due to its intriguing structure: the macrocyclic core imparts sufficient strain on the system to force one benzene rings to adopt a boat-shaped conformation, out...
Organic compounds which contain one or more nitrogen atoms are especially important as they are disproportionately represented among biologically active molecules. As a result, significant effort has been focused on the development of methods for the synthesis of nitrogenous molecules. We identified the aminal as an under-explored functional group. Despite...
In this report, three studies are presented that aid in the development of drug discovery and their synthesis. In each, the importance of the marriage between computations and experiments is highlighted. Continued efforts in this vein are essential for future efforts towards improving human health.
The first case study investigated...
Aminal radical intermediates were generated by the method of radical translocation and reacted in C-C bond forming reactions with electronically deficient alkenes (Schiedler et al. Org. Lett. 2012, 14, 6092). Aminal radical intermediates can participate in inter- and intra-molecular reactions using both Bu3SnH and (TMS)₃SiH as hydride donors. Carbon–carbon bonds...
Since the discovery of molecular chirality in 1848, this notion has had a substantial impact on medicine, biology, and chemistry. Extensive effort has been directed towards the construction of chiral molecules that contain sp³ hybridized stereogenic centers. In contrast, less effort has been dedicated to molecules that are chiral by...