Green Oxidation Catalysts for Fine Chemical Synthesis

EPA Grant Number: R829553
Title: Green Oxidation Catalysts for Fine Chemical Synthesis
Investigators: Shapley, Patricia A.
Institution: University of Illinois at Urbana-Champaign
EPA Project Officer: Savage, Nora
Project Period: January 1, 2002 through December 31, 2004
Project Amount: $325,000
RFA: Technology for a Sustainable Environment (2001) RFA Text |  Recipients Lists
Research Category: Sustainability , Pollution Prevention/Sustainable Development


Improvements in the environmental impact of the pharmaceutical and agricultural chemical industries have lagged improvements seen in the synthesis of bulk commodity chemicals. Fine chemicals are typically prepared by multistep reactions that use stoichiometric reagents and chiral auxiliaries. The atom economy of these syntheses is poor. Because many biologically active compounds from the pharmaceutical and agricultural chemical industries are highly oxygenated and prepared from simpler compounds by some type of oxidation reaction, there is a need for more selective oxidation catalysts.

This project will promote the environmentally responsible synthesis of fine chemicals through the development of a series of catalysts for the selective oxidation and modification of substrates. This will improve atom economy and reduce waste in one of the fastest growing areas of the chemical industry. By varying the metals and their ligands in heterometallic complexes {M(N)R2}2(µ -S)2M"Lx and [N(n-Bu)4][M(N)R2}(µ -O)2M'O2], we will create a "toolbox" of complexes with a range of steric and electronic properties.

Replacing petroleum-based feedstocks with renewable feedstocks from agricultural sources would reduce our dependence on foreign oil reserves, reduce the net release of CO2 into the atmosphere, and promote the agricultural industry in the United States. In order to use corn and soybean-derived compounds in the synthesis of fine chemicals, we must develop new, selective methods for their modification. In this project we focus on catalyzing oxidative transformations of fatty acids from corn and soybean oil, isoflavones from soy, and steroids from these plant sources. We will also prepare water-soluble catalysts for the oxidation of carbohydrates.

To lessen the need for volatile organic compounds as solvents, we will examine supercritical carbon dioxide as a reaction solvent. We will "heterogenize" some catalysts by attaching molecular species to an insoluble support. This should aid in the separation of catalyst from the product.

The first objective of this project is to synthesize a series of new heterometallic oxidation catalysts with a range of steric and electronic properties. Some complexes will be chiral to catalyze asymmetric oxidation reactions. Our goal is to prepare a "toolbox" of catalysts that would each be effective for the oxidation of only one functional group in a particular substrate. Molecular oxygen will be the only stoichiometric oxidant used. A second objective is to find methods for the chemical transformation of agricultural products to fine chemicals. We will test our new heterometallic complexes as catalysts for oxidative transformations of fatty acids from corn and soybean oil, isoflavones from soy, and steroids from these plant sources. We will also prepare water-soluble catalysts for the oxidation of carbohydrates. The final objective is to reduce the quantity of volatile organic solvents used in oxidation reactions. We will test water-soluble complexes for catalytic activity in water. Some complexes will be tested in alternative solvents, such as supercritical CO2. Supported metal complexes will be tested as heterogeneous catalysts.


We will generate a family of potential lipid oxidation catalysts of the formula {M(N)R2}2(µ -S)2M"Lx or [N(n-Bu)4][M(N)R2}(µ -O)2M'O2] by methods similar to those we have previously used to synthesize {Ru(N)Me2}2(µ-S)2Pt(dppe). Each new complex will be fully characterized and surveyed for oxidation of a range of substrates in the presence of molecular oxygen. Products will be quantified by GC or HPLC techniques. Those heterometallic complexes that prove to be selective oxidation catalysts in the initial survey will be examined as catalysts for the oxidation reactions of selected plant steroids, isoflavones, and carbohydrates with molecular oxygen. We will isolate the organic products and use NMR spectroscopy, mass spectrometry, and elemental analysis to characterize them.

Expected Results:

The results from this proposal would relate to the Technology for a Sustainable Environment program section 2.2.1: Chemistry and Chemical Reaction-based Engineering for Pollution Avoidance or Prevention. The design of more selective catalysts for the oxidation of organic substrates would greatly reduce waste. The use of molecular oxygen for these oxidations would reduce the chemical hazards associated with other oxidizing agents. The development of methods for the catalytic transformation of agricultural products into fine chemicals would reduce our need for non-sustainable, petroleum-based feedstocks.

Estimated Improvement: Successful completion of the work will lead to higher efficiency and lower waste in the production of fine chemicals.

Publications and Presentations:

Publications have been submitted on this project: View all 16 publications for this project

Journal Articles:

Journal Articles have been submitted on this project: View all 4 journal articles for this project

Supplemental Keywords:

VOC, pollution prevention, green chemistry, renewable, waste reduction, oxidation, environmental chemistry., RFA, Scientific Discipline, Sustainable Industry/Business, Chemical Engineering, Environmental Chemistry, cleaner production/pollution prevention, Sustainable Environment, Technology for Sustainable Environment, Chemistry and Materials Science, New/Innovative technologies, supercritical carbon dioxide (SCCO2) technology, renewable feedstocks, oxidation, waste reduction, oxidation reactions, fine chemicals, "toolbox" of catalyst, catalysts, supercritical carbon dioxide, catalytic transformations, agricultural industry, chemcial synthesis, carbon dioxide, solvent substitute, solvent replacements, pollution prevention, Volatile Organic Compounds (VOCs), chemical transformation, environmentally-friendly chemical synthesis, green chemistry, pharmaceutical industry, renewable resource, solvents, chemical synthesis

Progress and Final Reports:

2002 Progress Report
2004 Progress Report
Final Report