Generation of N,O-Divinylhydroxylamines and Use as Key Intermediates for Selective C–C Bond Formation in Cascade Reactions

Friday, January 28th, 2022 at 3:30 PM, transmitted in Hand 1134
via Zoom: https://uic.zoom.us/j/82908835614?pwd=QmZOdHVvZHNDck9PM1MyM3Fna0JEZz09
Meeting ID: 829 0883 5614    Passcode: PhvzC4KZ

Abstract: N,O-Divinylhydroxylamines are underutilized as synthetic intermediates for transferring stereochemical information. Although the Fischer-Indole reaction and the Piloty-Robinson pyrroline synthesis provide robust and elegant routes to privileged heterocycles, the key C-C bond forming step in these transformations is rarely used to set stereochemical information. The barrier to achieving this goal is the need to develop reactions that avoid formation thermodynamically-favored heterocyclic products and access analogous pathways to Claisen rearrangements where the facial selectivity of the pericyclic transition state can be used to install vicinal stereocenters. Our group has designed mild conditions and appropriate N-protecting groups to access N,O-divinylhydroxylamines and their inherent diastereoselective rearrangement reactivity. The use of this approach for accessing retrosynthetically distinct routes to 2-aminotetrahydrofurans and 1-pyrrolines will be discussed, in addition to mechanistic insight towards rearrangement pathways and the synthetic utility of unique rearrangement products.

Bio: Prof. Laura L. Anderson received her Ph.D. from UC Berkeley in 2005 where she worked in the groups of Prof. John Arnold and Prof. Robert G. Bergman. After completing an NIH postdoctoral fellowship with Prof. Keith A. Woerpel at UC Irvine, she began her independent career at the University of Illinois at Chicago in 2008 where she and her group have focused on designing transformations to use the reactivity imbedded in conjugate nitrones and hydroxylamines to address synthetic challenges. Prof. Anderson was promoted to Associate Professor in 2015 and has served as a Program Director /Expert in the Division of Chemistry at the National Science Foundation since 2019.

Hosted by:  Dr. Vicky Montiel