Drew University Library : University Archives : Theses and Dissertations
	author Beyza N. Yilmaz title Samarium Diiodide: Air-Free Synthesis Methods and Some Applications in Simple Reduction and Cross Coupling Reactions abstract Samarium diiodide (SmI2) is a powerful and versatile single electron reductant discovered by Henri B. Kagan in 1977. Over the years, it has found increasing applications in organic synthesis. Despite being a useful synthetic tool, it is underutilized in many synthetic chemistry laboratories due to limitations caused by its oxyphilicity that requires expensive equipment such as a glovebox to work with the reagent under inert conditions. The first part of this paper will show an easy and straightforward method for the synthesis of SmI2 without using a glovebox. Our method employs a Schlenk line to achieve inert microenvironments within reaction glassware. Using our Schlenk line technique we successfully developed a synthesis protocol for SmI2 that is reproducible. Simple reduction reactions with high yields well recorded in literature were carried out with freshly distilled SmI2. Gas chromatography and mass spectrometry were used to determine the % conversions of these reduction reactions which were used to back- calculate the concentration of samarium diiodide. The second part of the paper addresses synthetic applications of the reagent in the SmI2-mediated Barbier coupling reaction with three different Nickel (II) salts: NiI2 and Ni(acac)2 and Ni(dppe)2. Ni(II) salts in catalytic amounts were tested for their efficiency in catalyzing the reaction and selectively forming the Barbier coupling product. Results were analyzed using GC-MS. We have successfully formed the Barbier product using this strategy, however, GC data showed a mixture of products. Future work in our laboratory includes refining our protocol in order to successfully synthesize the desired Barbier product in high yields. After achieving our first goal, we aim to apply this catalytic approach to the Nozaki-Hiyama-Kishi reaction which is catalyzed by Cr(II) by replacing Cr(II) with Sm(II). This will ultimately provide a novel and greener approach to the NHK reaction by effectively replacing a toxic metal reducing agent with a non-toxic one. school The College of Liberal Arts, Drew University degree B.S. (2022) advisor Dr. Kimberly Choquette committee Dr. Mary-Ann Pearsall Dr. Roger Knowles full text BYilmaz.pdf