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Gregory C. Fu

 


Gregory C. Fu

Gregory C. Fu
Firmenich Professor of Chemistry


Room 18-290
(617) 253-2664
Fax: (617) 324-3611
gcf@mit.edu
Admin. Assistant: Susan Lydon
Tel: (617) 252-3882

Fu Research Group
B.S. Massachusetts Institute of Technology 1985
Ph.D. Harvard University 1991


Research Summary
Our research program is focused on the development of new reagents and methods for organic synthesis, with an emphasis on asymmetric catalysis. The achievement of our objectives requires an understanding of stereoselective synthesis, physical organic chemistry, and metal-based reactivity. Current areas of interest of our laboratory include asymmetric nucleophilic and nickel- and Lewis-acid catalysis, the design of new chiral ligands, and palladium-catalyzed coupling reactions.

Asymmetric catalysis. Due to the "handedness" of the molecules of life (peptides, DNA/RNA, carbohydrates, etc.), enantiomeric compounds often display quite different biological activity. The resulting need to efficiently generate compounds in enantiopure form (sales of enantiopure drugs in 2001: $147 billion) has led to burgeoning interest in asymmetric synthesis, and tremendous progress in this area has been achieved during the past few decades. Of course, stereoselective reactions that are based on chiral catalysts, rather than on stoichiometric chiral reagents or on substrate-bound chiral auxiliaries, can be advantageous from the standpoints of efficiency and economy. We are developing a wide array of asymmetric catalysts (e.g., based on Cu, Fe, and Rh), and we are applying them to a broad range of processes (e.g., acylation, cyclopropanation, hydrogenation, hydrosilylation, and isomerization).

Palladium-catalyzed coupling reactions. During the final quarter of the twentieth century, palladium catalysts emerged as extremely powerful tools for the construction of carbon–carbon bonds. Numerous monographs and review articles have documented the increasing frequency with which palladium-catalyzed coupling processes are applied to a diverse set of endeavors, ranging from synthetic organic chemistry to materials science.

Palladium-catalyzed processes have had a particularly significant impact on natural products synthesis. For example, the Suzuki (Losartan and terprenin), Heck (scopadulcic acid and taxol), and Stille (rapamycin and dynemicin) reactions have played pivotal roles in the total synthesis of a large number of complex bioactive molecules. Despite the tremendous accomplishments that have been achieved in the area of palladium-catalyzed carbon–carbon bond formation, it is nevertheless true that significant challenges remain. In order to enhance the utility of these coupling reactions, we are developing more active palladium catalysts that expand the scope of these processes (e.g., couplings of aryl chlorides and of alkyl halides/tosylates).

Recent Publications
Aminoalcohols as Ligands for Nickel-Catalyzed Suzuki Reactions of Unactivated Alkyl Halides, Including Secondary Alkyl Chlorides, with Arylboronic Acids
J. Am. Chem. Soc. 2006, 128, 5360–5361.
González-Bobes, F.; Fu, G. C.


Catalytic Enantioselective O–H Insertion Reactions
J. Am. Chem. Soc. 2006, 128, 4594–4595.
Maier, T. C.; Fu, G. C.


Umpolung of Michael Acceptors Catalyzed by N-Heterocyclic Carbenes

J. Am. Chem. Soc. 2006, 128, 1472–1473.
Fischer, C.; Smith, S. W.; Powell, D. A.; Fu, G. C.


Synthesis, Resolution, and Aldol Reactions of a Planar-Chiral Lewis Acid Complex
J. Am. Chem. Soc. 2005, 127, 15352–15353.
Liu, S.-Y.; Hills, I. D.; Fu, G. C.


Catalytic Asymmetric Synthesis of Piperidine Derivatives Through the [4+2] Annulation of Imines with Allenes
J. Am. Chem. Soc. 2005, 127, 12234–12235.
Wurz, R. P.; Fu, G. C.


Catalytic Asymmetric Staudinger Reactions to Form ß-Lactams: An Unanticipated Dependence of Diastereoselectivity on the Choice of the Nitrogen Substituent
J. Am. Chem. Soc. 2005, 127, 11586–11587.
Lee, E. C.; Hodous, B. L.; Bergin, E.; Shih, C.; Fu, G. C.


Kinetic Resolutions of Azomethine Imines via Copper-Catalyzed [3+2] Cycloadditions
J. Am. Chem. Soc. 2005, 127, 11244–11245.
Suárez, A.; Downey, C. W.; Fu, G. C.


Catalytic Asymmetric Synthesis of Esters from Ketenes
J. Am. Chem. Soc. 2005, 127, 6176–6177.
Wiskur, S. L.; Fu, G. C.


Catalytic Enantioselective Construction of All-Carbon Quaternary Stereocenters:
Synthetic and Mechanistic Studies of the C-Acylation of Silyl Ketene Acetals

J. Am. Chem. Soc. 2005, 127, 5604–5607.
Mermerian, A. H.; Fu, G. C.


Asymmetric Nickel-Catalyzed Negishi Cross-Couplings of Secondary a-Bromo Amides with Organozinc Reagents
J. Am. Chem. Soc. 2005, 127, 4594–4595.
Fischer, C.; Fu, G. C.


Stille Cross-Couplings of Unactivated Secondary Alkyl Halides using Monoorganotin Reagents
J. Am. Chem. Soc. 2005, 127, 510–511.
Powell, D. A.; Maki, T.; Fu, G. C..

 

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