Washington and Lee University Chemistry Department

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Marcia B. France, Ph. D. Chemistry California Institute of Technology Phone Number: (540) 458 - 8879 E-mail: francem@wlu.edu Office Number: A413

Courses Taught:

• Chem 241 Organic Chemistry I
• Chem 241 Organic Chemistry Laboratory I
• Chem 241S Organic Chemistry I at St. Andrews University, Scotland
• Chem 242 Organic Chemistry II
• Chem 242 Organic Chemistry Laboratory II
• Chem 243 Organic Spectroscopy
• Chem 243 Organic Spectroscopy Laboratory
• Chem 295B Culinary Chemistry
• Chem 347 Advanced Organic Chemistry
  

Research Interests:

The France group is interested in the development of transition metal complexes of chiral Schiff base ligands as catalysts for the asymmetric cyclopropanation of olefins by diazo compounds. The cyclopropane functionality occurs in commercial insecticides as well as many natural products of biological importance and can be converted into other organic functional groups. We have investigated one asymmetric cyclopropanation system in which the active catalyst is prepared in situ by the reaction of a chiral Schiff base ligand with one of several copper(I) precursors. When styrene is introduced to the reaction mixture followed by slow addition of ethyl diazoacetate, moderate enantioselectivities are observed. By modifying the substituents on the ligands, we have been able to achieve enantiomeric excesses greater than 50%, with E/Z ratios typically in the range 1.5-2.0. Even more noteworthy, we have also recently obtained promising results with several other metal precursors that are not commonly used in these types of reactions, including a ruthenium complex that, to our knowledge, has never been previously reported as a cyclopropanation catalyst precursor. This system gives enantiomeric excesses over 80% for the cyclopropanation of styrene. Our current research efforts are concentrated on identifying the active species in the ruthenium system in order to further improve its utility. We are also continuing to vary the substituents on the ligands and to investigate the use of other olefins and diazo compounds in both the copper and the ruthenium systems.

Research Students Supervised:

41 at W&L (Laura A. Adams, Divya Ajay, Jeffrey Bonham, James A. Browne, Hans T. Carlson, Rebecca A. Clark, David Cooper, Geoffrey C. Cooper, Elizabeth H. Cox, Laetitia Dalmazio (non-W&L volunteer), T. Markley Earl, W. Chadwick Ellis, Andrew Griffin, Paulianda Griffith, Veronica Griffith, Daniel G. Gurnon, Amanda Haines, Wesley A. Hoke, Marium G. Holland, H. Brooks Hooper, Eric D. Huttenbach, G-Yoon Jamie Im, Nicole Johnson, Angela J. Kim, Michael Kuntz, Yinghao Long, Allyn K. Milojevich, Yo Miura, Shane Newhouser, Laura K. Pekman, Patrick J. Renton, W. Michael Seganish, Emily P. Smith, H. Lesley Smith, Tracy A. Stitt, J. Turner Vosseller, Scott M. Wein, Michael Welsh, Ben Yemini, J. Kenneth Zelenak, John P. Zimmer)
2 at Caltech (David Mai, Susie Kohout)

Education

• 1994 Ph.D., Chemistry, California Institute of Technology Pasadena, CA
  • Thesis Advisor: Professor Robert H. Grubbs
  • Thesis Title: Olefin Metathesis with Group VIII Transition Metal Complexes: Mechanism, Reactivity, and Catalyst Development
• 1989 M.S., Chemistry, Yale University New Haven, CT
• 1988 S.B., Chemistry, Massachusetts Institute of Technology Cambridge, MA
  

Awards:

• 1999 Faculty Travel Award to attend the 1999 National Organic Symposium
• 1993 Associated Students of the California Institute of Technology Teaching Award
• 1991 Dow Travel Fellowship
• 1988 - 1991 National Science Foundation Predoctoral Fellowship
• 1988 Association of M.I.T. Alumnae Award for the Woman Who Has Shown the Highest Level of Scholastic Achievement in Her Graduating Class
• 1988 Alpha Chi Sigma Award
• 1988 American Institute of Chemists Award
• 1988 Society for Applied Spectroscopy Student Award

Professional Organizations:

• 1995 Council on Undergraduate Research
• 1995 Virginia Academy of Science
• 1988 Phi Beta Kappa
• 1985 Phi Lambda Upsilon, Honorary Chemical Society
• 1984 American Chemical Society

Grants:

• American Chemical Society Petroleum Research Fund - Undergraduate Faculty Sabbatical Grant; "Synthesis of Novel Nitrogen Ligands for Asymmetric Catalysis," July 2005-July 2006, $50,000.
• Jeffress Memorial Trust Research Grant; "Chiral Schiff Base Complexes as Catalysts for Asymmetric Cyclopropanation," July 1998 - 1999, $19,200; Renewal Grant, January 2004-December 2004, $10,000; Renewal Grant, January 2005-December 2005, $10,000.
• C.B. Fleet Company, Inc. "Kinetics Studies of the Hydrolysis of Bisocodyl," January 1, 2004 - December 31, 2004, $41,000 (with Steven G. Desjardins).
• National Science Foundation Major Research Instrumentation grant; "Multinuclear Gradient Inverse Probe, Amplifier, and Overnight Low Temperature Dewar for High-Field NMR Spectroscopy in the Chemistry Department at Washington and Lee University," August 2003- August 2006, $70,830 (with Erich S. Uffelman (project director), Steven G. Desjardins, and Lisa T. Alty).
• National Science Foundation Research Opportunity Award to support sabbatical leave at Stanford University, August 2000 - August 2001, $18,000 (with Robert M. Waymouth).
• Japan Society for the Promotion of Science Postdoctoral Fellowship for American Researchers; "Asymmetric Organic Reactions in Chiral Ionic Liquids," awarded January 2000, but declined.
• Research Corporation Cottrell College Science Award; "Novel Chiral C₃ Symmetric Tripodal Isocyanide Ligands," June, 1997 - June, 1999, $30,330.
• American Chemical Society Petroleum Research Fund; "Chiral Schiff-Base Complexes as Catalysts for Asymmetric Cyclopropanation," September, 1996-September, 1998, $20,000.
• National Science Foundation Instrumentation and Laboratory Improvement grant; "High-Field Multinuclear NMR In Undergraduate Education at Washington and Lee University," 1996-1998, $99,500 (with Erich S. Uffelman, Lisa T. Alty, and Steven G. Desjardins).

Publications:

• France, M. B.; Fuentes, J. A.; Slawin, A. M. Z.; Clarke, M. L. "Iridium Complexes of Chiral Diamines Containing Carbon and Nitrogen Stereocentres: Synthesis, Structure, and Evaluation as Transfer Hydrogenation Catalysts" Manuscript in preparation for Dalton Trans.
• Diaz Valenzuela, M. B.; Clarke, M. L; France, M. B.; Gunn, M. E. "A Novel Tridentate Ruthenium Complex for Asymmetric Hydrogenation and Transfer Hydrogenation of Bulky Ketones"; Manuscript in preparation for J. Org. Chem.
• Clarke, M. L.; France, M. B. "The Carbonyl Ene Reaction: An Atom Efficient C-C Bond Forming Reaction in Organic Synthesis" Invited manuscript submitted to Tetrahedron.
• Clarke, M. L.; Jones, C. E. S.; France, M. B. "The First Organocatalytic Carbonyl-Ene Reaction: Isomerisation-Free C-C Bond Formations Catalysed by H-Bonding Thio-ureas" Beilstein J. Org. Chem. 2007, 3: 24.
• Clarke, M. L.; France, M. B.; Knight, F. R.; Frew, J. J. R.; Roff, G. J. "Enantio- and Diastereo-selective Hydrogenation of a Fluorinated Diketone"; Synlett 2007, 11, 1739-1741.
• Clarke, M. L.; France, M. B.; Fuentes, J. A. Milton, E. J.; Roff, G. J. "A Convenient Catalyst System for Microwave Accelerated Cross-Coupling of a Range of Aryl Boronic Acids with Aryl Chlorides"; Beilstein J. Org Chem. 2007, 3:18.
• Wilmes, G. M.; France, M. B.; Lynch, S. R.; Waymouth, R. M. "Effects of Ligand Substitutions on the Rotation Rate of Indenyl Ligands in bis(2-arylindenyl)zirconocenes by NMR Lineshape Analysis and Relaxation in the Rotating Frame"; Organometallics 2004, 23(10), 2405-2411.
• France, M. B.; Milojevich, A. K.; Stitt, T. A.; Kim, A. J. "High Trans Selectivity in the Copper Bis(oxazoline) Catalyzed Asymmetric Cyclopropanation of Olefins by Trimethylsilyl Diazomethane"; Tetrahedron Lett. 2003, 44(52), 9287-9290.
• Holland, M. G.; Griffith, V. E.; France, M. B.; Desjardins, S. G. "Kinetics of the Ring-Opening Metathesis Polymerization of a 7-Oxanorbornene Derivative by Grubbs Catalyst"; J. Polym. Sci., Part A: Polym. Chem. 2003, 41(13), 2125-2131.
• France, M. B.; Alty, L. T.; Earl, T. M. "Synthesis of a 7-oxanorbornene Derivative: A Two-Step Sequence Preparation for the Organic Laboratory"; J. Chem. Educ. 1999, 76, 659.
• France, M. B.; Uffelman, E. S. "Ring-Opening Metathesis Polymerization with a Well-Defined Ruthenium Carbene Complex: An Experiment for the Undergraduate Inorganic or Polymer Laboratory"; J. Chem. Educ., 1999, 76, 661.
• Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. "A Series of Well-Defined Metathesis Catalysts - Synthesis and Applications of RuCl2(=CHR')(PR3)2"; Angew. Chem. Int. Ed. Engl. 1995, 34, 2039.
• France, M. B.; Feldman, J.; Grubbs, R. H. "An Iridium-based Catalyst System for Metathesis/Isomerization of Acyclic Olefins, including Methyl Oleate"; J. Chem. Soc., Chem. Commun. 1994, 1307.
• France, M. B.; Paciello, R. A.; Grubbs, R. H. "Initiation of Ring-Opening Metathesis Polymerization in Protic Media. Extension of [Ru(H2O)6]2+ Catalyzed Polymerization to Less-Strained Cyclic Monomers"; Macromolecules 1993, 26, 4739.
• France, M. B.; Grubbs, R. H.; McGrath, D. V.; Paciello, R. A. "Chain Transfer During the Aqueous Ring-Opening Metathesis Polymerization of 7-Oxanorbornene Derivatives";
• Macromolecules 1993, 26, 4742.
• Grubbs, R. H.; Novak, B. M.; McGrath, D. V.; Benedicto, A.; France, M. B.; Nguyen, S. T. "Ruthenium ROMP Catalysts"; Polymer Preprints 1992, 33(1), 1225.
• Jacobsen, E. N.; Marko, I.; France, M. B.; Svendsen, J. S.; Sharpless, K. B. "Kinetic Role of the Alkaloid Ligands in Asymmetric Catalytic Dihydroxylation"; J. Am. Chem. Soc. 1989, 111, 737.

Patents:

• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; Singapore Patent 51411. Request for Certificate of Correction paperwork filed February 2008.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; European Patent 1375506, filed August 1, 1996. Certificate of Correction issued February 2008.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; European Patent 0842200. Certificate of Correction issued February 2008.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; Japanese Patent Application 2004-137844. Request for Certificate of Correction paperwork filed November 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; Chinese Patent 96197372.2, filed August 1, 1996. Certificate of Correction issued December 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; Chinese Patent Application 200610101678.4, filed August 1, 1996. Certificate of Correction issued December 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; U. S. Patent 7,102,047, filed October 18, 2004, issued September 5, 2006. Certificate of Correction issued May 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; U. S. Patent 6,806,325, filed December 19, 2002, issued October 19, 2004. Certificate of Correction issued December 2006.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; U. S. Patent 6,515,084, filed December 21, 2000, issued February 4, 2003. Request for Certificate of Correction filed July 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; U. S. Patent 6,111,121, filed January 15, 1998, issued August 29, 2000. Request for Certificate of Correction filed July 2007.
• Grubbs, R. H,; Schwab, P.; Nguyen, S. T.; France, M. B. "High Metathesis Activity Ruthenium and Osmium Metal Carbene Complexes"; U. S. Patent 5,831,108, filed July 31, 1996, issued November 3, 1998. Certificate of Correction issued August 2006.
• Feldman, J.; France, M. B. "Iridium Catalysts for Metathesis of Acyclic Olefins"; U. S. Patent 5,403,802, 1995.
• Feldman, J.; France, M. B. "Metathesis of Acyclic Olefins Using an Iridium/Silver Catalyst Composition"; U. S. Patent 5,352,812, 1994.

Undergraduate researchers are listed in italicized type.