faculty

Associate Professor of Chemistry
Ph.D., California Institute of Technology

New Synthetic Methods, Catalysis and Asymmetric Catalysis, Organometallic Chemistry

Phone:(734) 615-0451
E-mail: mssanfor@umich.edu

Research Group

Research in my group focuses on problems at the interface of organic and inorganic chemistry. In particular, we work to discover, understand, and exploit the unique (and often highly selective) reactions between organic substrates and transition metal centers in order to address current challenges in organic synthesis and catalysis. Some problems of particular interest involve the development of environmentally benign, catalytic approaches to the enantioselective synthesis of heterocycles and halocyclopropanes, the aerobic, asymmetric oxidation of olefins, the stereoselective formation/elaboration of metal enolates, and the activation/functionalization of C-H and C-F bonds. In all of these catalytic systems, we aim to achieve high efficiency coupled with high levels of regio-, diastereo-, enantio-, and chemoselectivity. Students in my group will gain experience in the synthesis and characterization of organic and organometallic compounds, the discovery of new reactions, and the application of these new reactions in organic synthesis and catalysis. Importantly, our research relies heavily on mechanistic investigations to direct both the development and optimization of catalytic processes. Several representative projects are detailed briefly below.

Catalysts for the Aerobic Synthesis of Chiral Heterocycles
A first area of research involves the design of novel transition metal catalysts for the enantioselective synthesis of chiral heterocycles (e.g., epoxide, aziridine, pyrrolidine, and benzofuran derivatives), which serve as valuable building blocks in asymmetric synthesis. Our approach also addresses a long-standing challenge in catalysis - the development of reactions that use dioxygen as a terminal oxidant. In particular, these systems provide inexpensive and environmentally friendly routes for the oxidation of olefins to heterocycles with O₂ in conjunction with simple amines, alcohols, or water as sources of functionality. The mechanism of these reactions differs dramatically from traditional "atom-transfer" olefin oxidation, and we are interested in probing the effects of this unusual mechanistic manifold on enantioselectivity, catalyst longevity, and substrate scope in order to develop catalysts that will find widespread application in synthetic chemistry. Catalysts for the Stereoselective

Synthesis of Halocyclopropanes
Chiral cyclopropanes represent an important structural motif in natural products that display a wide range of biological activities, and stereochemically well-defined halocyclopropanes can serve as versatile building blocks for the divergent and stereoselective construction of substituted cyclopropyl moieties. This project involves the development of catalysts for the stereoselective assembly of chiral halocyclopropanes from olefins and halocarbenoid precursors. We are interested in investigating both practical and mechanistic aspects of this new transformation as well as in applying this methodology to the synthesis of a series of complex and synthetically useful cyclopropane derivatives.

Oxidative Functionalization of Hydrocarbons
A third area of research involves the development of general and practical methods for the regio- and chemoselective oxidative functionalization of unactivated hydrocarbons. Our approach to this longstanding problem involves coupling directed C-H bond activation with oxidative insertion into the resulting metal alkyl. The scope, functional group compatibility, and mechanism of both stoichiometric and catalytic versions of this transformation are under investigation. We are also working to demonstrate the utility of these methods in both individual and tandem reaction sequences directed at the multi-component assembly of complex molecules.

AWARDS

• Research Corporation Cottrell Scholar Award-2006
• AstraZeneca Excellence in Chemistry Award-2006
• 2005 (NIH) Presidential Early Career Awards for Scientists & Engineers
• Bristol-Myers-Squibb Unrestricted Grant in Synthetic Organic Chemistry-2005
• Alfred P. Sloane Research Fellow -2005
• 2005 National Science Foundation Career Award.
• 2005 Lilly Grantee Award in Organic Chemistry
• 2004 Boehringer Ingelheim New Investigator Award in Organic Chemistry
• Beckman Young Investigator Award (2004)
• 2003 Camille & Henry Dreyfus New Faculty Award
• NIH NRSA Postdoctoral Fellowship
• Herbert Newby McCoy Award for Graduate Research
  

REPRESENTATIVE PUBLICATIONS

1. Dick, A.R.; Kampf, J.; Sanford, M. S. “Platinum Model Studies for Palladium-Catalyzed Oxidative Functionalization of C–H Bonds,” Organometallics, 2005, 24, 482.
2. Dick, A. R.; Hull, K. L.; Sanford, M. S."A Highly Selective Catalytic Method for the Oxidative Functionalization of C-H Bonds" J. Am. Chem. Soc. 2004, 126, 2300-2301.
3. Sanford, M. S.; Groves, J. T. "Anti-Markovnikov Hydrofunctionalization of Olefins Mediated by Rhodium Porphyrins," Angew. Chem., Int. Ed. 2004, 43, 588-590.
4. Trnka, T. M.; Morgan, J. P.; Sanford, M. S.; Wilhelm, T. E.; Scholl, M.; Choi, T.-L.; Ding, S.; Day, M. W.; Grubbs, R. H. "Synthesis and Reactivity of Ruthenium Alkylidene Complexes Coordinated with Phosphine and N-Heterocyclic Carbene Ligands" J. Am. Chem. Soc. 2003, 125, 2546-2558.
5. Sanford, M. S.; Love, J. A.; Grubbs, R. H. "Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts," J. Am. Chem. Soc. 2001, 123, 6543-6554.
6. Sanford, M. S.; Henling L. M.; Day, M. W.; Grubbs, R. H. "Ruthenium-Based Four-Coordinate Olefin Metathesis Catalysts," Angew. Chem., Int. Ed. 2000, 39, 3451-3454.