Development of a Synthetic Strategy Toward Falcatin A. Development of an Asymmetric Diels–Alder Reaction of α-Acyloxy Enones

Citation

Mendoza, Skyler Dakota (2022) Development of a Synthetic Strategy Toward Falcatin A. Development of an Asymmetric Diels–Alder Reaction of α-Acyloxy Enones. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/v3ys-kj69. https://resolver.caltech.edu/CaltechTHESIS:11062021-003540914

Abstract

Accessing natural products via de novo synthetic methods is important for the discovery of new medicines, antibiotics, agrochemicals, and more. Design and investigation of efficient strategies is of interest to many pharmaceutical industries.

Herein, we discuss several strategies geared towards the synthesis of the natural product falcatin A. First, a general discussion of the class of natural products is discussed. Secondly, we discuss our first generation photoredox cascade cyclization approach toward the synthesis of falcatin A. This strategy allows for the efficient and convergent synthesis of two halves of falcatin. Next, a transition metal-catalyzed cascade cyclization approach is discussed in which we were able to successfully synthesize the core of the natural product on a model system. Efforts are ongoing to elaborate to more advanced fragments for the synthesis of falcatin A. Lasty, we discuss our work on the yttrium-catalyzed asymmetric Diels–Alder reaction of α-acyloxy enone dienophiles, performed in collaboration with BASF. We demonstrate that this methodology can be utilized to access enantioenriched natural product T-4-ol.

Thesis Files