Chemistry at Illinois University of Illinois at Urbana-Champaign

M. Christina White

Professor of Chemistry

Professor M. Christina White received her B.A. with highest honors in Biochemistry from Smith College in 1992 and her Ph.D. from Johns Hopkins University in 1998. After a postdoctoral fellowship at Harvard University, she joined the faculty there in 2002. In 2005 she joined the faculty at the University of Illinois at Urbana-Champaign. Her research interests are in the field of organic synthesis with an emphasis on the discovery of transition-metal mediated reactions that address unsolved problems in organic methodology.

To view the White Group twitter page visit: https://twitter.com/MCWhiteGroup

Research

Among the frontier challenges in chemistry in the 21st century are (1) increasing control of chemical reactivity and (2) synthesizing complex molecules with higher levels of efficiency. Although it has been well demonstrated that given ample time and resources, highly complex molecules can be synthesized in the laboratory, too often current methods do not allow chemists to match the efficiency achieved in Nature. This is particularly relevant for molecules with non-polypropionate-like oxidation patterns (e.g. Taxol). Traditional organic methods for installing oxidized functionality rely heavily on acid-base reactions that require extensive functional group manipulations (FGMs) including wasteful protection-deprotection sequences. Due to their ubiquity in complex molecules and inertness to most organic transformation, C—H bonds have typically been ignored in the context of methods development for total synthesis. My laboratory has initiated a program to develop highly selective oxidation methods, similar to those found in Nature, for the direct installation of oxygen, nitrogen and carbon functionalities into allylic and aliphatic C—H bonds of complex molecules and their intermediates. Unlike Nature which uses elaborate enzyme active sites, we rely on the subtle electronic and steric interactions between C—H bonds and small molecule transition metal complexes to achieve high selectivities. Gaining a fundamental and predictive understanding of these interactions through mechanistic studies is one of the main goals and discovery engines of our research. Using these methods, my group aims to develop novel strategies for streamlining the process of complex molecule synthesis. Collectively, we aim to change the way that complex molecules are constructed by redefining the reactivity principles of C—H bonds in complex molecule settings. Please see the White Group website for more details.

Publications

Paradine, S.M.; Griffin, J.R.; Zhao, J.P.; Petronico, A.L.; Miller, S. M.; White, M.C. "A Manganese Catalyst for Highly Reactive Yet Chemoselective Intramolecular C(sp3)—H Aminations." Nature Chemistry 2015, 7, 987.

Gormisky, P.E.; White, M.C. "Catalyst-Controlled Aliphatic C--H Oxidations with a Predictive Model for Site-Selectivity." J. Am. Chem. Soc. 2013, 135, 14052.

Paradine, S.M.; White, M.C. "Iron-Catalysed Intramolecular Allylic C--H Amination." J. Am. Chem. Soc. 2012, 134, 2036.

Bigi, M.A.; Reed, S.A.; White, M.C. "Diverting non-haem iron catalysed aliphatic C--H hydroxylations towards desaturations." Nature Chemistry 2011, 3, 216.

Chen, M.S.; White, M.C. "Combined Effects on Selectivity in Fe-Catalyzed Methylene Oxidation." Science 2010, 327, 566.

Stang, E.M.; White, M.C. "Total Synthesis and Study of 6-deoxyerythronolide B via Late-stage C-H Oxidation". Nature Chemistry, 2009, 1, 547.

Young, A.Y.; White, M.C. "Catalytic Intermolecular Allylic C-H Alkylation." J. Am. Chem. Soc. 2008, 130, 14090.

Chen, M.S.; White, M.C. "A Predictably Selective Aliphatic C-H Oxidation Reaction for Complex Molecule Synthesis." Science, 2007, 318, 783-787.

Fraunhoffer, K.J.; White, M.C. "syn-1,2-Amino Alcohols via Diastereoselective Allylic C-H Amination." J. Am. Chem. Soc. 2007, 129, 7274-7276.

Awards

  • Mukaiyama Award, 2016
  • Fellow of the Royal Society of Chemistry, 2014
  • Royal Society of Chemistry Merck Award, 2013
  • AAAS Fellow, 2012
  • Cope Scholar Award, 2009
  • Roche Excellence in Chemistry Award, 2009
  • Abbott Young Investigator Award, 2008
  • AstraZeneca Excellence in Chemistry Award, 2008
  • Camille Dreyfus Teacher Scholar Award, 2008
  • Amgen Young Investigator Award, 2008
  • Boehringer Ingelheim Pharmaceuticals New Investigator Award, 2008
  • Bristol-Myers Squibb "Unrestricted Grant in Synthetic Organic Chemistry", 2008-2009.
  • Pfizer Award for Creativity in Organic Chemistry, 2008-2009
  • Eli Lilly Grantee Award, 2007-2009
  • Alfred P. Sloan Research Fellow, 2008-2010
  • Fellow, UIUC Center for Advanced Study, 2006
  • NSF CAREER Award, 2006-2010
  • Camille and Henry Dreyfus New Faculty Award, 2002-2007
  • National Institutes of Health Postdoctoral Fellowship, 1999-2002
  • American Chemical Society Predoctoral Fellowship, 1997-1998

Highlights

Publication Highlights

For highlights of a highly reactive yet chemoselective manganese catalyst see:

For highlights of the first catalyst-controlled aliphatic C--H oxidation (JACS 2013, 135, 14052) see:

  • Jake Yeston "Tell O Where to Go", Editors Choice Science 2013, 342, 15.
  • Kathryn Roberts, "Better than an Enzyme", Chemistry & Industry 2013, October 1st issue
  • Stu Borman, "Catalysts Calls the Shots"
    , News of the Week: C&E News 2013, 91(40), 12.
  • Karl Collins, "Oxidation Station", Opinions, Chemistry World, Jan. 8, 2014
  • News Article: Diana Yates, "New Small Molecule Catalyst Does Work of Many Enzymes", UIUC News Bureau, e! Science News, Health Medicine Network

Huw Davies: "Expanding the Art of Synthesis." Nature Chemistry 2009, 1, 519.

For Highlights in C&E News and Chemistry World on our C-H oxidative macrolactonization approach to the classic erythronolide core see: Totally Unusual Synthesis and New Approach to a Classic Structure.

Recent article on work in the White Group in C&E News: http://pubs.acs.org/isubscribe/journals/cen/86/i30/html/8630sci1.html

For a Highlight of our intermolecular linear allylic amination reaction see: Yamamoto, H.; Naodovic, N. "Heterobimetallic Catalyst for Intermolecular C-H Amination". Synfacts, 2008, 603.

For a historical and synthetic perspective on our aliphatic C-H oxidation reaction see: M. Christmann, "Selective Oxidation of Aliphatic C-H Bonds in the Synthesis of Complex Molecules." Angew. Chem. Int. Ed. 2008, 47, 2740.

"Science Concentrate Highlight" in Chemical & Engineering News: "Revised Amination Skips Olefin Tether." Chem. Eng. News, 2008, 86 (11), 42.

"A Predictably Selective Aliphatic C-H Oxidation Reaction for Complex Molecule Synthesis" by Chen, M.S.; White, M.C. was highlighted in the following publications:

  • Nature : "Green Cleaver." Nature 2007, 450 (8), 139.
  • Chemistry & Industry: Patrick Walter "Green Catalyst Could Clean Up in Drug Production." Chemistry & Industry 2007, 21, 7.
  • Science: R.H. Crabtree, "No Protection Required." Science, 2007, 318, 756.
  • "News of the Week" highlight in Chemical & Engineering News: Jyllian Kemsley, "Catalyst Oxidizes Selectively." Chem. Eng. News, 2007, 85 (45), 8.
  • Chemistry World: Richard Van Noorden, "Step Change for Organic Synthesis.", Chemistry World, 2007.
  • Technology Review: Kevin Bullis, "Drugs That Are Easier on the Environment." Technology Review, 2007.

"syn-1,2-Amino Alcohols via Diastereoselective Allylic C-H Amination." by Fraunhoffer, K.J. and White, M.C. was recently highlighted in the following publications:

"Sequential Hydrocarbon Functionalization: Allylic C-H Oxidation/Vinylic C-H Arylation," by Delcamp, J.H. and White, M.C. was featured in an oxidation methods review in Annu. Rep. Prog. Chem., Sect. B, 2007, 103, 35-46.

"Serial Ligand Catalysis: A Highly Selective Allylic C-H Oxidation" by Chen, M.S.; Prabagaran, N.; Labenz, N. and White, M.C. received commentary in Science and Technology Concentrate in Chem. & Eng. News 2005, 83, 31.

"Hydrocarbon Oxidation vs. C-C Bond Forming Approaches for Efficient Syntheses of Oxygenated Molecules" by Fraunhoffer, K. J.; Bachovchin, D.A. and White, M.C. was reviewed and recognized in the following publications:

  • This article was selected by the Organic Letters Editorial Board as one of the 9 best Organic Letters articles in 2004.
  • For an excellent review highlighting this synthetic strategy see: Hoffmann, R.H. "Protecting-Group-Free Synthesis." Synthesis 2006, 3531.

Other Highlights

Dr. White and Sean A. Reed's work in developing the first catalytic intermolecular allylic C-H amination reaction has been reviewed in C&E News. Read the C&E News article here.

Patents

Photo of M. Christina White