Synthesis, Vinylation and Rearrangement of NH-Isoxazolines and Copper Catalyzed 6 Pi Electrocyclization

Enaminones are a privileged motif that have both nucleophilic and electrophilic reactivity embedded within. Finding new ways to access these compounds is of high interest. The Anderson group is interested in utilizing [3,3] sigmatropic rearrangements to access new N-heterocycles in diastereoselective fashion. The work described in Chapter 1 features a new method for accessing enaminones utilizing a cascade approach that features an N–vinylisoxazoline intermediate that undergoes [3,3] sigmatropic rearrangement to form densely functionalized exocyclic vinylogous pyrrolidines. The functionalization of these compounds showcased a unique reactivity at the gem-dione under basic conditions and the mechanism of the corresponding products was further investigated. Chapter 2 discusses a ring expansion reaction of azetidine–N–oxides to form highly functionalized isoxazolidine products with up to 3 contiguous stereocenters in excellent diastereoselectivity. The scope was explored and shown to be tolerant for a wide array of aniline nucleophiles as well as a limited number of amines and alcohols with various azetidine–N–oxides. Chapter 3 is centered around establishing a method for copper catalyzed 6 π electrocyclization to form morpholines and morpholine–N–oxides via an initial Chan–Lam coupling followed by spontaneous electrocyclization.

Author dc:creator

• Dylan Cole Keane (24399965)

• Methodology

Statement dc:rights

• In Copyright
• Open Access after 2028-05-01

DOI dc:identifier

https://doi.org/10.25417/uic.32994977.v1

OAI identifier oai:identifier

oai:figshare.com:article/32994977