59th Annual Report on Research 2014

During the most recent grant period, we have continued developing new applications for the Mitsunobu reaction. More specifically, we have been engaged in the preparation of N,N-diethylbenzamides owing to their heavy involvement in directed-ortho-metalation (DoM) reactions for the incorporation of numerous functional groups onto aromatic scaffolds. Additionally, we believe that our variant of the Mitsunobu reaction proceeds via a non-classical mechanism involving the intermediacy of an acyloxyphosphonium ion rather than the commonly accepted alkoxyphosphonium ion.

Previously we had struggled to find conditions to afford clean reaction products from our recently discovered application of the Mitsunobu reaction to prepare N,N-diethylbenzamides. After an exhaustive search of the chemical literature, we were pleased to find that a relatively straightforward acid-base extraction procedure employing 1 M sodium hydroxide (NaOH). As a result of our optimal work-up conditions, we were able to successfully obtain pure reaction products for a wide-range of starting benzoic acids as outlined in Table 1.

With our ability to obtain clean reaction products now in-hand, we are currently investigating the mechanism of this non-classical application of the Mitsunobu reaction employing ¹H, ¹³C, and ³¹P NMR experiments.

Impact on Undergraduate Students and PI:

Nearly all of the chemistry majors at Sewanee: The University of the South would like to pursue a summer research opportunity on campus in order to strengthen their understanding of fundamental chemical principles as well as bolster their laboratory skills — benefits that are increasingly important to developing a successful graduate/medical school application. However, summer research opportunities are in high demand on our campus. While Sewanee has been increasing funding for summer research opportunities, there is never enough funding for every request. While we are proud of the level of research activity at Sewanee, we recognize that every year several interested and highly motivated students are not able to participate due to a lack of funding. This ACS-PRF grant has provided an important opportunity for our students to gain valuable research experience in the chemical sciences. Because of the importance that the undergraduate research experience plays in students' decisions to pursue graduate study, this ACS grant may also have a significant impact on motivating even more of our students to pursue graduate study in chemistry.

The PI has an active and productive research program supported entirely by extramural funding from both private and federal agencies. Dr. Pongdee is a staunch advocate of the education through research paradigm and has made engaging undergraduate students in independent research projects a priority during his academic career. This ACS-PRF grant has enabled the PI to provide competitive funds for undergraduate summer research stipends, the purchase of chemical reagents, and consumable supplies. Furthermore, this grant has enabled the PI to remain intellectually engaged, while also allowing his research students to gain invaluable experience in communicating science, within the discipline while traveling to present research findings at conferences and symposia.