New Synthetic Applications of N-Arylnitrones and N-Aryloxyphthalimides

2019-08-06T00:00:00Z (GMT) by Michelle A Kroc
My thesis is comprised of two parts. First, the Anderson group has developed a tunable cascade reaction to access a variety of different N- heterocycles from α,β-unsaturated N-arylnitrones and electron-deficient allenes. Due to the constant demand for new N-heterocycles for medicinal and material applications, we are focused on leveraging this system for the rapid divergent synthesis of new compounds containing the indole motif. The cascade reaction is proposed to proceed via common intermediates that can be directed towards dihydrocarbazoles, dihydropyridoindoles, bicyclic benzazepinones, and functionalized indoles through the careful selection of the corresponding hydrogen-bond donor or Lewis acid catalysts. The second part of my thesis addresses our method for the dioxygenation of alkenylboronic acids and the synthesis of α-oxygenated ketones using N-hydroxyphthalimide as mild oxidant via a copper- mediated C–O bond forming reaction and a [3,3]-sigmatropic rearrangement. We extended this reactivity to arylboronic acids for the synthesis of catechols. This approach would allow the regioselectivity of the catechol synthesis to be determined by the constraints of the [3,3]-rearrangement as opposed to the electron-density of the aryl ring.