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2000 Progress Report: Catalysts for Environmentally Benign Organic Reactions in Water
EPA Grant Number: R826120Title: Catalysts for Environmentally Benign Organic Reactions in Water
Investigators: RajanBabu, T. V.
Institution: Ohio State University - Main Campus
EPA Project Officer: Karn, Barbara
Project Period: November 1, 1997 through October 31, 2000 (Extended to November 16, 2001)
Project Period Covered by this Report: November 1, 1999 through October 31, 2000
Project Amount: $280,000
RFA: Technology for a Sustainable Environment (1997)
Research Category: Pollution Prevention/Sustainable Development
Description:
Objective:The use of water as an environmentally friendly solvent for the manufacture of chemical intermediates depends on the discovery of new catalysts and processes. The primary objective of this project is the design and development of broadly applicable water-soluble organometallic catalysts. A second objective highly relevant to green chemistry is to discover and develop new, highly selective and catalytic reactions in which abundantly available carbon feedstocks, such as ethylene and propylene, can be used for the synthesis of pharmaceutical and agricultural intermediates. Progress Summary:
Use of Water as a Solvent for Organic Synthesis: Development of Water-Soluble Organometallic Catalysts from Carbohydrates. Ability of metal ions to catalyze selective reactions depends on the ligands to which they are attached. We envisioned the use of carbohydrates, the most readily available natural products, as scaffolding for the preparation of water-soluble metal complexes. The expectation was that once a metal-sequestering group (in the present case, a trivalent phosphorus atom) was appropriately incorporated on a carbohydrate frame, the resulting ligand would be water soluble. Because there are thousands of carbohydrate molecules to choose from, there exists the possibility of optimizing the catalytic properties of the metal for efficiency and selectivity.
During the first year of this grant, we developed a broadly applicable synthesis of two classes of water-soluble rhodium complexes from readily available derivatives of sugars, D-salicin, x, x-trehalose, and D-mannitol. Applications of these complexes for the synthesis of highly valued amino acids by rhodium-catalyzed hydrogenation reactions of dehydroamino acids in water have been demonstrated.
During the past year (1999-2000), the syntheses of a series of phospholane
ligands from another readily available sugar, D-mannitol, was completed. These
ligands can be converted easily into water-soluble hydroxyphosphines. The
catalytic applications of the complexes of these ligands currently are under
study. Preliminary indications are that they are among the best ligands
for three prototypical reactions: rhodium-catalyzed hydrogenation of enamides
and dehydroamino-acids (C-H bond-forming reaction) and palladium-catalyzed
allylation reactions (a C-C bond-forming reaction).
Use of Ethylene/Propylene for Fine Chemical Synthesis. Recently, we discovered a new protocol for a nickel-catalyzed codimerization reaction, in which unprecedented yields and selectivity were achieved in the addition of ethylene (1 atmosphere, low temperature, 0.003 equivalents of the nickel catalyst, >95 percent yield) to a variety of substituted styrenes. The products of this environmentally friendly reaction (catalytic use of the metal, no side-products, ambient conditions) are useful for the synthesis of widely used antiinflammatory agents such as ibuprofen, flurbiprofen, and naproxen. Other potential applications of the resulting products include synthesis of high-melting polymers.
We can make one of the two enantiomers (left-handed and right-handed mirror image forms) of the antiinflammatory agents preferentially using ligands derived from readily available sugars. This is an important discovery because it is well known that only one of the two forms (in this case, the left-handed form) of these molecules have the desired pain-killing ability. Yet, except for naproxen (the active ingredient in ALEVE) all these drugs are sold as a mixture of the two forms.
A study of the basic chemistry associated with this process has allowed us to develop other potentially important applications of this chemistry. Two of them are: (1) a high-yielding addition of propylene to vinylarenes; and (2) catalyzed cyclization of x, w-dienes for the synthesis of cyclic compounds. Cyclic compounds are ubiquitous in organic chemistry, and selective synthesis of these compounds from readily available precursors is always a challenge.
Future Activities:During the first 2 years of this project, we have established the basic protocols for the preparation and use of a number of water-soluble ligands and their Rh complexes. In the next phase of the project, we plan to expand this chemistry to include other metal complexes (ruthenium, palladium, platinum, and nickel) and other reactions: rhodium- and ruthenium-catalyzed hydrogenation of common substrates like imines, ketones, and acrylic acids, rhodium-catalyzed hydroformylation reactions (use of carbon monoxide in synthesis), and palladium-catalyzed cross-coupling reactions.
In the area of ethylene/propylene-codimerizations, we will try to expand the scope of the activated olefins (dienes, strained olefins) that would take part in the reaction.
Journal Articles on this Report : 9 Displayed | Download in RIS Format
| Other project views: | All 22 publications | 13 publications in selected types | All 12 journal articles |
| Type | Citation | ||
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Clyne DS, Mermet-Bouvier YC, Nomura N, RajanBabu TV. Substituent effects on ligands on asymmetric induction in a prototypical palladium-catalyzed allylation reaction: Making both enantiomers of a product in high optical purity using the same source of chirality. Journal of Organic Chemistry 1999;64(20):7601-7611 |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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Jin J, RajanBabu TV. Heterodimerization of propylene and vinylarenes: Functional group compatibility in a highly efficient Ni-catalyzed carbon-carbon bond-forming reaction. Tetrahedron 2000;56(15):2145-2151 |
R826120 (1999) R826120 (2000) |
not available |
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Nandi M, Jin J, RajanBabu TV. Synergistic effects of hemilabile coordination and counterions in homogeneous catalysis: new tunable monophosphine ligands for hydrovinylation reactions. Journal of the American Chemical Society 1999;121:9899-9900. |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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Radetich B, RajanBabu TV. Catalyzed cyclization of alpha,omega-dienes: A versatile protocol for the synthesis of functionalized carbocyclic and heterocyclic compounds. Journal of the American Chemical Society 1998;120(31):8007-8008 |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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RajanBabu TV, Radetich B, You KK, Ayers TA, Casalnuovo AL, Calabrese JC. Electronic effects in asymmetric catalysis: Structural studies of precatalysts and intermediates in Rh-catalyzed hydrogenation of dimethyl itaconate and acetamidocinnamic acid derivatives using C-2-symmetric diarylphosphinite ligands. Journal of Organic Chemistry 1999;64(10):3429-3447 |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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RajanBabu TV, Nomura N, Jin J, Radetich B, Park HS, Nandi M. Hydrovinylation and related reactions: New protocols and control elements in search of greater synthetic efficiency and selectivity. Chemistry-A European Journal 1999;5(7):1963-1968 |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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Shin S, RajanBabu TV. Water-soluble organometallic catalysts from carbohydrates. 1. Diarylphosphinite-Rh complexes. Organic Letters 1999;1:1229-1232. |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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Yan Y, RajanBabu TV. Highly flexible synthetic routes to functionalized phospholanes from carbohydrates. Journal of Organic Chemistry 2000;65. |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
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Yan YY, RajanBabu TV. Ligand tuning in asymmetric catalysis: Mono- and bis-phospholanes for a prototypical Pd-catalyzed asymmetric allylation reaction. Organic Letters 2000;2(2):199-202 |
R826120 (1999) R826120 (2000) R826120 (Final) |
not available |
innovative technology, environmentally conscious manufacturing, homogeneous catalysis, pharmaceutical intermediates, organic chemistry in water, carbon feedstocks, waste minimization. , Sustainable Industry/Business, Scientific Discipline, RFA, Technology for Sustainable Environment, Sustainable Environment, Chemical Engineering, cleaner production/pollution prevention, Environmental Chemistry, environmentally benign water cycles, cleaner production, catalysts, green chemistry, ligands, carbon bond formation, environmentally conscious manufacturing, green process systems, hydrogeneration, SIC = pharmaceutical , transition metal catalysts
Progress and Final Reports:
1999 Progress Report
Original Abstract
Final Report