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The Study of Organometallic Calcium Complexes and the Development of Calcium-Catalyzed Reactions. Efforts Towards the Development of the sp2-sp3 Nickel-Catalyzed Heck Reaction

Vanden Eynden, Matthew James
http://rave.ohiolink.edu/etdc/view?acc_num=osu1306705769

Abstract Details

2011, Doctor of Philosophy, Ohio State University, Chemistry.
This dissertation will entail the research that was performed and the data that was developed during my five year graduate career while enrolled at The Ohio State University (2006-2011). This Ph.D. track program has led to my development as a competent and capable scientist, worthy of the distinction ‘doctor’ and confident in his abilities to perform at a high level in any aspect of or at any institution within my chemistry career. This dissertation will discuss two main projects. The first project that was bestowed upon me at this university was the development of a new chemical method in which alkyl sp3 halides are reacted with sp2 alkenes in a non-traditional Heck reaction. Since the typical Heck reaction is well-studied extensively utilized, and knowing that sp3 halides undergo facile elimination and subsequent decomposition of starting material, bridging this gap and allowing for this synthetic transformation to exist would serve as a fundamental reaction in the toolbox of an organic chemist. We wanted to utilize an electron-poor nickel center to facilitate the ‘alkyl Heck’ reaction. Using our proposed metal center and using modified literature conditions we decided that this reaction was capable of being performed. Indeed, there was some success in the reaction, but only achieving a 49% isolated yield. Our drawback in this system was that nickel metal sources tend to undergo side reactions, and leftover starting materials, developed products and other reaction intermediates were succumbing to alkene couplings and olefin reductions. These reactions were complicating the reaction mixture with a substantial amount of isolable, but detrimental, bi-products. We have proposed, though, methods to negate this result and our laboratory is practicing this new series of methods in due course. The second and main project that will be discussed involves the use of calcium salts and alkoxides to act as catalysts for the transformations of standard organic chemistry reactions. In particular, we have developed a novel calcium complex capable of promoting the Pictet-Spengler reaction of 3-hydroxysubstituted phenethylamines with various aldehydes and ketones, giving a very broad scope of unnatural tetrahydroisoquinoline alkaloids. This catalyst and the various other catalysts created during the course of this project are mostly novel and are developed, isolated and characterized in our labs, a feat in which other labs do not normally undertake. During this campaign, our knowledge of calcium in general has skyrocketed and continues to grow day by day. This is a very underdeveloped field of chemistry and, when utilized properly, provides a safe, clean and inexpensive alternative to traditional catalytic methods. Calcium has a unique ability to act as both a Lewis acid and Brønsted base in these such reactions, making the activity of calcium not only hard to diagnose, but very diverse at the same time. We have found that our simple calcium complexes are capable of performing transformations encompassing a wide variety of chemical reactions. With more time and study, hopefully the ultimate goal of calcium as a catalyst in organic synthesis will be realized and the movement from drying agent to inexpensive surprisingly-active catalyst can be achieved.
James Stambuli, PhD (Advisor)
T.V. Rajanbabu, PhD (Committee Member)
Jon Parquette, PhD (Committee Member)
Charles Klein, PhD (Committee Member)
220 p.
Chemistry
calcium; Pictet-Spengler; Heck

Recommended Citations

Citations

  • Vanden Eynden, M. J. (2011). The Study of Organometallic Calcium Complexes and the Development of Calcium-Catalyzed Reactions. Efforts Towards the Development of the sp2-sp3 Nickel-Catalyzed Heck Reaction [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1306705769

    APA Style (7th edition)

  • Vanden Eynden, Matthew. The Study of Organometallic Calcium Complexes and the Development of Calcium-Catalyzed Reactions. Efforts Towards the Development of the sp2-sp3 Nickel-Catalyzed Heck Reaction. 2011. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1306705769.

    MLA Style (8th edition)

  • Vanden Eynden, Matthew. "The Study of Organometallic Calcium Complexes and the Development of Calcium-Catalyzed Reactions. Efforts Towards the Development of the sp2-sp3 Nickel-Catalyzed Heck Reaction." Doctoral dissertation, Ohio State University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=osu1306705769

    Chicago Manual of Style (17th edition)

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© 2011, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.