SEP 16, 2015 12:00 PM PDT

The Functionalization of C-H Bonds

Speakers
  • Professor of Chemistry, University of Illinois
    Biography
      M. Christina White was born in Athens, Greece. She received a B.A. degree in biochemistry with highest honors from Smith College working with Stuart Rosenfeld. After a one-year stint in the biology graduate program working with Christian Anfinsen, she received her Ph. D. degree from Johns Hopkins University in chemistry with Gary Posner as an ACS Medicinal Chemistry predoctoral fellow. She conducted postdoctoral studies at Harvard University with Eric Jacobsen as an NIH postdoctoral fellow and is currently a Professor of Chemistry at the University of Illinois at Urbana-Champaign.



      The White group aims to discover selective, catalytic C-H oxidation, amination, and alkylation reactions for use in organic synthesis. They have contributed novel palladium/sulfoxide [(http://en.wikipedia.org/wiki/White_catalyst), Aldrich, Strem, and TCI] and iron catalysts [(http://en.wikipedia.org/wiki/White-Chen_Catalyst) Aldrich,Strem] that functionalize allylic and aliphatic C-H bonds under preparative conditions with predictable site-selectivities and without the requirement for directing groups. These catalysts led to the discovery of a code for differential reactivity between C-H bonds based on electronic, steric, and stereoelectronic effects that has been demonstrated to be general across a range of different aliphatic C-H oxidation reactions. Using these catalysts, seminal demonstrations of site-selective and -divergent C-H oxidations in complex molecules pioneered the concept of late-stage functionalization.

    Abstract:
    Among the frontier challenges in chemistry in the 21st century are the interconnected goals of increasing control of chemical reactivity while synthesizing and diversifying complex molecules with higher efficiency. Traditional organic methods for installing oxidized functionality rely heavily on sequential acid-base reactions that require extensive functional group manipulations (FGMs). In contrast, nature routinely uses allylic and aliphatic C-H oxidation methods, generally mediated by heme and non-heme iron monooxygenase enzymes, to directly install oxidized functionality into preformed frameworks of complex molecules. Due to their ubiquity in complex molecules and inertness to most organic transformations, C-H bonds have typically been ignored in the context of methods development for total synthesis. The exceptions to this rely on substrate directing groups to facilitate site-selectivity and reactivity. The discovery and development of catalysts for the direct installation of oxygen, nitrogen and carbon into allylic and aliphatic C-H bonds are discussed. Unlike Nature which uses elaborate shape or functional group recognition active sites, these small molecule catalysts utilize differential sensitivity to the C-H bond electronics, sterics, and stereoelectronic environment to achieve predictable site-selective and -divergent oxidations in complex molecule settings- and without the requirement for directing groups. Using these catalysts a code for site-selective C-H reactivity has been delineation that has proven to be highly general across a range of C-H oxidation catalysts and reactions. Our current understanding of these interactions and the development of a catalyst reactivity model that calculates and even predicts the major site of oxidation as well as the magnitude and direction of the site-selectivity in complex substrates as a function of catalyst will be described.

    Show Resources
    You May Also Like
    NOV 18, 2019 07:00 AM PST
    Add to Calendar Select one of the following: iCal Google Calendar Outlook Calendar Yahoo Calendar
    C.E. CREDITS
    NOV 18, 2019 07:00 AM PST
    Add to Calendar Select one of the following: iCal Google Calendar Outlook Calendar Yahoo Calendar
    DATE: November 18, 2019TIME: 7:00am PST, 11:00am EST, 4:00pm CEWT How often do you pipette in your cell culture lab every day? Usually, we do it so often that we tend stop th...
    AUG 13, 2019 09:00 AM PDT
    C.E. CREDITS
    AUG 13, 2019 09:00 AM PDT
    DATE: August 13, 2019TIME: 9:00am PT, 12:00pm ET, 5:00pm BST Molecular complexes are major constituents of cells, hence unraveling their mechanisms is key to fuller comprehension of c...
    OCT 02, 2019 11:00 AM PDT
    OCT 02, 2019 11:00 AM PDT
    DATE: October 2, 2019TIME: 11:00am PDT, 2:00pm EDT Ditch the Excel spreadsheets and manage your molecular workflows entirely in your LIMS Achieve configuration of molecular workf...
    OCT 16, 2019 10:00 AM PDT
    Add to Calendar Select one of the following: iCal Google Calendar Outlook Calendar Yahoo Calendar
    OCT 16, 2019 10:00 AM PDT
    Add to Calendar Select one of the following: iCal Google Calendar Outlook Calendar Yahoo Calendar
    DATE: October 16, 2019TIME: 9:00am PDTManual titrations can be extremely challenging and frustrating, impeding your efficiency in the lab. More importantly, these issues can lead to inc...
    MAY 16, 2019 04:00 PM CEST
    C.E. CREDITS
    MAY 16, 2019 04:00 PM CEST
    DATE: May 16, 2019TIME: 7:00am PDT, 10:00am EDT, 4:00pm CEST The emergence of NGS is revolutionizing the microbiological sciences and transforming medicine. Deep sequencing has...
    SEP 05, 2019 04:00 PM CEST
    C.E. CREDITS
    SEP 05, 2019 04:00 PM CEST
    DATE: September 5, 2019TIME: 7:00am PT, 10:00am ET, 4:00pm CEST PCR (Polymerase Chain Reaction) has gone through a massive evolution since its development in 1983. Besides it...
    Loading Comments...
    Show Resources