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Pd/C-catalyzed Suzuki cross- and self- couplings & the development of a lab-scale hydrogenation system
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Title
Pd/C-catalyzed Suzuki cross- and self- couplings & the development of a lab-scale hydrogenation system
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http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.17253
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ETD_708
Language
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English
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theses
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Chemical and Biochemical Engineering
Subject
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Topic
Palladium catalysts
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Topic
Hydrogenation
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Topic
Catalysis
Abstract
Suzuki couplings have become an efficient and clean strategy for the preparation of biologically active functionalized biphenyls, which are important building blocks for pharmaceutical and agricultural compounds. Among all catalysts of choice for Suzuki couplings, palladium on carbon (Pd/C) is most frequently used for industrial applications due to its high catalytic activity, low cost and easy removal from the reaction mixture. Using a model coupling reaction of biphenylacetic acid, we intended to provide a thorough understanding of Pd/C-catalyzed Suzuki couplings for a straightforward industrial implementation.
A detailed investigation of the reaction parameters was carried out in Chapter 2. The experimental observations indicate that excess amount of the borate is helpful to accelerate the reaction and 2 moles eq. of a strong base is the best choice for the reaction. Furthermore, our results suggest that transmetalation is the rate-limiting step of the Pd/C-catalyzed Suzuki couplings and also show that [OH-] is a critical factor affecting the reaction rate.
In Chapter 3, the mechanism of Pd-leaching from Pd/C was investigated. The filtration test was used to prove that oxidative addition of aryl-bromides is the main cause for Pd-leaching, which is independent of the reaction solvent and temperature. In addition, the oxidative addition of aryl-borates is another cause for Pd-leaching. PVPy adsorption studies suggest that the activity of Pd/C is mainly due to leached Pd. Furthermore, PVPy was proven to be a good reagent for complete removal of Pd-residuals from the reaction mixture.
In Chapter 4, homocoupling of arylboronic acids was successfully carried out with Pd/C in water/2-propanol (9:1 in volume ratio) under air, to obtain symmetric biaryls in good yield. This novel system was discovered during Pd-leaching studies and optimized in our work. The experimental observations suggest that higher water fractions in the co-solvent and higher reaction temperature are beneficial for the reaction. DFT calculations suggest that the overall reactivity of the different arylboronic acids is independent of the oxidative addition of Pd to the arylboronic acid.
Lastly, we successfully established a lab-scale hydrogenation system at Rutgers University to carry out chiral hydrogenation, which is presented in Chapter 5. The system allows reactions operated under 120 bars at a wide range of reaction temperatures (-80~350??C).
A detailed investigation of the reaction parameters was carried out in Chapter 2. The experimental observations indicate that excess amount of the borate is helpful to accelerate the reaction and 2 moles eq. of a strong base is the best choice for the reaction. Furthermore, our results suggest that transmetalation is the rate-limiting step of the Pd/C-catalyzed Suzuki couplings and also show that [OH-] is a critical factor affecting the reaction rate.
In Chapter 3, the mechanism of Pd-leaching from Pd/C was investigated. The filtration test was used to prove that oxidative addition of aryl-bromides is the main cause for Pd-leaching, which is independent of the reaction solvent and temperature. In addition, the oxidative addition of aryl-borates is another cause for Pd-leaching. PVPy adsorption studies suggest that the activity of Pd/C is mainly due to leached Pd. Furthermore, PVPy was proven to be a good reagent for complete removal of Pd-residuals from the reaction mixture.
In Chapter 4, homocoupling of arylboronic acids was successfully carried out with Pd/C in water/2-propanol (9:1 in volume ratio) under air, to obtain symmetric biaryls in good yield. This novel system was discovered during Pd-leaching studies and optimized in our work. The experimental observations suggest that higher water fractions in the co-solvent and higher reaction temperature are beneficial for the reaction. DFT calculations suggest that the overall reactivity of the different arylboronic acids is independent of the oxidative addition of Pd to the arylboronic acid.
Lastly, we successfully established a lab-scale hydrogenation system at Rutgers University to carry out chiral hydrogenation, which is presented in Chapter 5. The system allows reactions operated under 120 bars at a wide range of reaction temperatures (-80~350??C).
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xv, 124 pages
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Ph.D.
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Includes bibliographical references (p. 116-122).
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Chen
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Jeng-Shiou
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Jeng-Shiou Chen
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Johannes
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Johannes Khinast
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Henrik
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Henrik Pedersen
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Marianthi Ierapetritou
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Krogh-Jespersen
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Karsten
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Karsten Krogh-Jespersen
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Rutgers University
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Graduate School - New Brunswick
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2008
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2008-01
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Graduate School - New Brunswick Electronic Theses and Dissertations
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doi:10.7282/T3GH9JB4
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ETD doctoral
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Jeng-Shiou Chen
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Rutgers University. Graduate School - New Brunswick
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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